WO 2015/021991 Al

(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)

(19) World Intellectual PropertyOrganization

International Bureau(10) International Publication Number

(43) International Publication Date WO 2015/021991 Al19 February 2015 (19.02.2015) P O P C T

(51) International Patent Classification: DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,A 53/00 (2006.01) HN, HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,

KZ, LA, LC, LK, LR, LS, LT, LU, LY, MA, MD, ME,(21) International Application Number: MG, MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ,

PCT/DK20 14/050243 OM, PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA,

(22) International Filing Date: SC, SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM,

15 August 2014 (15.08.2014) TN, TR, TT, TZ, UA, UG, US, UZ, VC, VN, ZA, ZM,ZW.

(25) Filing Language: English(84) Designated States (unless otherwise indicated, for every

(26) Publication Language: English kind of regional protection available): ARIPO (BW, GH,

(30) Priority Data: GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, SZ, TZ,

PA 2013 00470 16 August 2013 (16.08.2013) DK UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,

(71) Applicant: CHEMINOVA A/S [DK/DK]; Thyboranvej EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, FT, LT, LU, LV,78, DK-7673 Harbo0re (DK). MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,

TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,(72) Inventor: OTTESEN, Lars Korsgaard; Mimersvej 80,

KM, ML, MR, NE, SN, TD, TG).DK-7620 Lemvig (DK).

Declarations under Rule 4.17 :(74) Agents: RASMUSSEN, Torben Ravn et al; AwapatentA S, Rigensgade 11, DK-13 16 K0benhavn K (DK). — as to applicant's entitlement to apply for and be granted a

patent (Rule 4.1 7(H))(81) Designated States (unless otherwise indicated, for every

kind of national protection available): AE, AG, AL, AM, Published:AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, — with international search report (Art. 21(3))BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,

(54) Title: COMBINATION OF 2-METHYLBIPHENYL-3-YLMETHYL (Z)-(lR)-CIS-3-(2-CHLORO-3,3,3-TRIFLUOROPROP-l-ENYL)-2,2-DIMETHYLCYCLOPROPANECARBOXYLATE WITH AT LEAST ONE INSECTICIDE, ACARICIDE, NEMATODE AND/OR FUNGICIDE.

¾ (57) Abstract: Presented are new pesticidal mixtures comprising 2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-3-(2-chloro-3,3,3-tri-fluoroprop-l-enyl)-2,2-dimethyl-cyclopropanecarboxylate and one or more of compound(s) (Π) which is an insecticide, acaricide,nematicide and/or fungicide. The invention relates also to methods and use of these mixtures for controlling harmful pests such as

¾ insects, arachnids, nematodes and fungi e.g. in and on plants, and for protecting such plants being infested with pests and also forprotecting seeds.

Combination of 2-methylbiphenyl-3-ylmethyl (Z)-(17?)-czs-3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate with at least one

insecticide, acaricide, nematicide and/or fungicide.

Introduction

The invention relates to new pesticidal mixtures comprising a pyrethroid

compound (I) which is (2-methylbiphenyl-3-ylmethyl (Z)-(1 )-c -3-(2-chloro-

3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate) and one or

more compounds (II) chosen among insecticides, acaricides, nematicides and/or

fungicides. The invention relates also to a method and use of these mixtures for

controlling harmful pests (e.g. insects, arachnids, nematodes and fungi) e.g. in

and on plants and non-crops, and for protecting such plants being infested with

pests and also for protecting seeds.

Background

One typical problem arising in the field of pest control lies in the need to reduce

the dosage rates of the active ingredient in order to reduce or avoid unfavorable

environmental or toxicological effects whilst still allowing effective pest

control.

Another problem encountered concerns the need to have available pest control

agents which are effective against a broad spectrum of pests.

There also exists the need for pest control agents that combine knock-down

activity with prolonged control, that is, fast action with long lasting action.

Another difficulty in relation to the use of pesticides is that the repeated and

exclusive application of an individual pesticidal compound leads in many cases

to a rapid selection of pests which have developed natural or adapted resistance

against the active compound in question. Therefore there is a need for pest

control agents that help prevent or overcome resistance.

It was therefore an object of the present invention to provide pesticidal mixtures

which solves at least one of the discussed problems such as reducing the dosage

rate, enhancing the spectrum of activity or combining knock-down activity with

prolonged control or as to resistance management.

It has been found that this object is in part or in whole achieved by the

combination of active compounds defined at the outset. Moreover, it has been

found that simultaneous, that is joint or separate, application of an active

compound (I) and one or more compounds (II) or successive application of an

active compound (I) and one or more compounds (II) allows enhanced control

of pests compared to the control rates that are possible with the individual

compounds.

The pesticidal active compound bifenthrin is a racemic mixture comprised of

mainly two isomers out of 8 possible due to the Z/E configuration on the vinyl

group and the two chiral centers on the cyclopropane ring (IRS, 3RS), i.e.

present in the molecule 2-methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate. One of these 8

isomers being the compound (I). Bifenthrin is primarily a mixture of the two

compounds 2-methylbiphenyl-3-ylmethyl (Z)-(17?)-czs-3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropane-carboxylate and 2-

methylbiphenyl-3-ylmethyl (Z)-(lS )-c -3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-

2,2-dimethylcyclopropane-carboxylate. On a commercial scale, bifenthrin is

produced according to methods that provide such mixtures, and the single most

active isomer is not easily separated.

It is known that the pesticidal effect of bifenthrin is found primarily in one of the

isomers, i.e. compound (I), as described by Liu et al. in Toxicolgy 253 (2008)

pp. 89-96; in Chirality 17 (2005) pp 127-133; and in United States Defensive

Publication no. T 107001. One would expect that when combining bifenthrin

with another pesticide, the same combination would require approximately half

the amount of the most active isomer (i.e. compound (I)) to provide the same

pesticidal effect. However, it has now surprisingly been found that an improved

effect is observed when substituting bifenthrin (including any of the other

isomers) with the compound (I), preferably substantially free of any of the

others isomers of (2-methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3 -trifluoroprop-

l-enyl )-2,2-dimethylcyclopropane-carboxylate. That is, it has been found that an

improved synergistic effect is present for pesticidal mixtures comprising the

compound (I) over same mixtures comprising bifenthrin.

The unexpected finding has important implications, both economical but also

environmental in that the pesticidal mixtures as herein described need only to be

applied at a lower dose and without the presence of potentially detrimental

isomers. It is a standard demand in crop protection to achieve an optimal effect

with active ingredients at the lowest dosage rate required while simultaneously

keeping the pollution of the environment as low as possible.

Description of the invention

The present invention relates to a mixture comprising compound (I) which is 2-

methylbiphenyl-3-ylmethyl (Z)-( 1 )-c -3-(2-chloro-3,3,3 -trifluoroprop-l-enyl)-

2,2-dimethylcyclopropanecarboxylate and one or more compound(s) (II) which

is either an insecticide, nematicide, acaricide or fungicide.

One aspect of the invention relates to a mixture comprising, as pesticidal active

ingredients, the compound (I) and just one other compound (II) which is an

insecticide, nematicide, acaricide or fungicide, i.e. a mixture containing the

compound (I) and one other compound (II) which is an insecticide, nematicide,

acaricide or fungicide as the sole active ingredients. Preferably the compound

(II) is an insecticide, nematicides or acaricide and most preferably an insecticide

or acaricide.

Another apect of the invention relates to a mixture comprising, as pesticidal

active ingredients, the compound (I) and just two other compounds (II) which

are selected among insecticides, nematicides, acaricides and/or fungicides, i.e. a

mixture containing the compound (I) and two other compounds (II) which are

selected among insecticides, nematicides, acaricides and/or fungicides as the

sole active ingredients. Preferably at least one of the two compound (II) is a

insecticide or an acaricide. More preferably the second of the two compounds

(II) is chosen among insecticides, nematicides or acaricides; with insecticides

and acaricides being of particular use. In another aspect the two compounds (II)

are both insecticides, nematicides, acaricides or fungicides, more preferably the

two compounds (II) are both insecticides, nematicides or acaricides and most

preferably the two compounds (II) are both insecticides or acaricides.

Compound (I) is preferably substantially free of any other isomer of 2-

methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-

dimethylcyclopropanecarboxylate.

Preferably the mixture of 2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-3-(2-

chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate and

one or more compounds (II) is substantially free of any other isomer of

2-methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3-trifluoroprop- l-enyl)-2,2-


More preferably the mixture of 2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-3-(2-

chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate and

one or more compounds (II) is substantially free of 2-methylbiphenyl-3-

ylmethyl (Z)-(lS )-c -3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-


With respect to the term "substantially free of any other isomer" as used herein,

it shall be understood that the composition contains a greater proportion or

percentage of 2-methylbiphenyl-3-ylmethyl (Z)-(17?)-czs-3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate, on a weight basis,

in relation to any other isomer of 2-methylbiphenyl-3-ylmethyl 3-(2-chloro-

3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate, these

percentages being based on the total amount of 2-methylbiphenyl-3-ylmethyl 3-

(2-chloro-3 ,3 ,3 -trifluoroprop- 1-enyl)-2,2-dimethylcyclopropanecarboxylate

present.

In a preferred embodiment, the term "substantially free of any other isomer" as

used herein means that the composition contains at least 70% by weight of 2-

methylbiphenyl-3-ylmethyl (Z)-( 1 )-c -3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-

2,2-dimethyl-cyclopropanecarboxylate, and 30% by weight or less of any of the

other isomers of 2-methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3-trifluoroprop-

l-enyl)-2,2-dimethylcyclopropanecarboxylate.

In a more preferred embodiment, the term "substantially free of any other

isomer" means that the composition contains at least 80% by weight of 2-


2,2-dimethylcyclopropanecarboxylate, and 20% by weight or less of 2-


2,2-dimethylcyclopropanecarboxylate or any other isomer.

In a still more preferred embodiment, the term "substantially free of any other

isomer" means that the composition contains at least 90% by weight of 2-


2,2-dimethylcyclopropanecarboxylate, and 10% by weight or less of 2-


2,2-dimethylcyclopropanecarboxylate or any other isomer.

In an even more preferred embodiment, the term "substantially free of any other

isomer" means that the composition contains at least 91%, preferably at least

92%, more preferably 93% by weight of 2-methylbiphenyl-3-ylmethyl Z - IR)-

c -3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropane-

carboxylate in relation to 2-methylbiphenyl-3-ylmethyl (Z)-(lS)-cz' -3-(2-chloro-

3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate or any other

isomer, even more preferably at least 94%, and most preferably at least 95%. In

a most preferred embodiment, the term "substantially free of any other isomer"

means that the composition contains at least 96%, preferably at least 97%, more

preferably at least 98% by weight of 2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-

3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate in

relation to 2-methylbiphenyl-3-ylmethyl (Z)-(lS)-cz' -3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate or any other isomer,

even more preferably at least 99%, and most preferably at least 99.5%.

To produce compound (I) (2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-3-(2-

chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate) on an

industrial scale it is desirable to find methods of making the final product that

avoid the use of expensive reagents and have as few chemical stages as possible.

A process for the preparation of compound (I) is provided comprising

a) chlorinating (Z)-(1 )-c -3-(2-chloro-3,3,3-trifluoro-l-propenyl)-2,2-dimethyl

cyclopropanecarboxylic acid (compound A) to give (Z)-(1 )-c -3-(2-chloro-

3,3,3-trifluoro-l-propenyl)-2,2-dimethyl cyclopropanecarboxylic acid chloride

(compound B) and

b) esterifying (Z)-(1 )-c -3-(2-chloro-3,3,3-trifluoro-l-propenyl)-2,2-dimethyl

cyclopropanecarboxylic acid chloride (compound B) with the (2-methyl-[l,l'-

biphenyl]-3-yl)methanol (compound C).

(Z)-(1 )-c -3-(2-chloro-3,3,3-trifluoro-l-propenyl)-2,2-dimethyl

cyclopropanecarboxylic acid (compound A) is a known compound and its

preparation is described for example in patent publication nos. US 4,683,089;

WO 02/06202; WO97/03941 and WO/9942432.

(2-methyl-[l,l'-biphenyl]-3-yl)methanol (compound C) is a known compound

and its preparation is described for example in CN 102603485 and CN 1935761.

Accordingly, the compound (I) may be produced as outlined in the below

reaction scheme:

Step a) is performed by standard techniques as in 'March 4th Edition - p .437-

38'. Preferred chlorinating agents are thionyl chloride, phosgene or phosphorous

oxychloride. Preferred solvents are hydrocarbons such as toluene, hexane,

heptane or fluorobenzene. Preferred temperatures are from ambient to 100 °C or

the boiling point of the solvent.

Step b) is performed in the presence of a solvent or in the absence of a solvent,

in which case the molten product can act as the reaction medium. The reaction

can be carried out in a single organic phase or in a mixture of a water

immiscible organic phase and an aqueous phase. The acid chloride, either neat

or in a solvent, may be added to the (2-methyl-[l,l'-biphenyl]-3-yl)methanol, or

the vice versa, but it is preferable to add the acid chloride to the (2-methyl-[l,l'-

biphenyl]-3-yl)methanol. The mol ratio of the reactants is preferably 1:1 but up

to 10 mol % excess of either reactant can be employed, but most preferably the

excess of one reactant over the other is 1-5 mol .

The reaction sequence can be performed step-wise, e.g. with isolation of the

acid-chloride (B) prior to reaction with compound (C), but overall the

compound (I) may also be prepared by a one-pot process, e.g. without isolation

of the intermediates.

The present invention relates therefore in one aspect to pesticidal mixtures

comprising as active compounds

1) A compound (I) which is 2-methylbiphenyl-3-ylmethyl (Z)-(lR)-cis-3-(2-

chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopropanecarboxylate,

preferably substantially free of any other isomer of 2-methylbiphenyl-3-

ylmethyl (17?S)-3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-dimethylcyclopro-

panecarboxylate

And

2) one or more further active ingredients (II) selected among compounds having

insecticidal, nematicidal and/or acaricidal activity, e.g. selected from the

following subgroups (1) to (29) (according to IRAC Mode-Of-Action

classification):

(1) Acetylcholinesterase (AChE) inhibitors e.g. Carbamates such as alanycarb,

aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim,

carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate,

furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl,

pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb,

XMC, and xylylcarb; or organophosphates such as acephate,

azamethiphos, azinphos (-methyl, -ethyl), cadusafos, chlorethoxyfos,

chlorfenvinphos, chlorfenvinphos, chlormephos, chlorpyrifos (-methyl),

coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/DDVP,

dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion,

ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate,

heptenophos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl)

salicylate, isoxathion, malathion, mecarbam, methamidophos,

methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-

methyl, parathion (-methyl), phenthoate, phorate, phosalone, phosmet,

phosphamidon, phoxim, pirimiphos (-methyl), profenofos, propetamphos,

prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep,

tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos,

triclorfon, and vamidothion;

(2) GABA-gated chloride channel antagonists e.g. Organochlorines such as

chlordane, endosulfan (alpha-); or fiproles (phenylpyrazoles) such as

ethiprole, fipronil, pyrafluprole, and pyriprole;

(3) Sodium channel modulators/voltage-dependent sodium channel blockers

e.g. Pyrethroids such as acrinathrin, allethrin (d-cis-trans, d-trans),

bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin,

cycloprothrin, cyfluthrin (beta-), cyhalothrin (gamma-, lambda-),

cypermethrin (alpha-, beta-, theta-, zeta-), cyphenothrin [(lR)-trans-

isomers], deltamethrin, dimefluthrin, empenthrin [(EZ)-(lR)-isomers),

esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,

flumethrin, fluvalinate (tau-), halfenprox, imiprothrin, metofluthrin,

permethrin, phenothrin [(lR)-trans-isomer), prallethrin, profluthrin,

pyrethrin (pyrethrum), resmethrin, RU 15525, silafluofen, tefluthrin,

tetramethrin [(lR)-isomers)], tralomethrin, transfluthrin and ZXI 8901; or

DDT; or methoxychlor;

(4) Nicotinergic acetylcholine receptor agonists e.g. Chloronicotinyls such as

acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram,

thiacloprid, thiamethoxam; or nicotine;

(5) AUosteric acetylcholine receptor modulators (agonists) e.g. spinetoram and

spinosad;

(6) Chloride channel activators e.g. the avermectins/milbemycins including

abamectin, aversectin C, doramectin, emamectin(-benzoate), eprinomectin,

ivermectin, lepimectin, selamectin, moxidectin and milbemectin;

(7) Juvenile hormone mimics e.g. hydroprene, kinoprene, methoprene,

fenoxycarb or pyriproxyfen;

(8) gassing agents including methyl bromide and other alkyl halides; or

chloropicrin; sulfuryl fluoride; borax; tartar emetic;

(9) Selective homopteran feeding blockers such as pymetrozine or flonicamid;

(10) Mite growth inhibitors e.g. lofentezine, diflovidazin, hexythiazox,

etoxazole;

(11) Microbial disruptors of insect midgut membranes e.g. Bacillus

thuringiensis subspecies israelensis, Bacillus sphaericus, Bacillus

thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies

kurstaki, Bacillus thuringiensis subspecies tenebrionis, and BT crop

proteins: CrylAb, CrylAc, CrylFa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb,

Cry34/35Abl;

(12) Inhibitors of mitochondrial ATP synthase e.g. diafenthiuron; or organotin

miticides such as azocyclotin, cyhexatin, and fenbutatin oxide; or

propargite; tetradifon;

(13) Uncouplers of oxidative phoshorylation via disruption of the proton

gradient including Chlorfenapyr, and DNOC;

(14) Nicotinic acetylcholine receptor channel blockers such as bensultap,

cartap hydrochloride, thiocyclam, and thiosultap- sodium;

(15) Inhibitors of chitin biosynthesis, type 0, e.g. Benzoylureas such as

bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron,

hexaflumuron, lufenuron, novaluron, noviflumuron, penfluron,

teflubenzuron, and triflumuron;

(16) Inhibitors of chitin biosynthesis, type 1 e.g. buprofezin;

(17) Moulting disruptors e.g. Cyromazine;

(18) Ecdysone receptor agonists/disruptors e.g. Diacylhydrazines such as

chromafenozide, halofenozide, methoxyfenozide, and tebufenozide;

(19) Octopamine receptor agonists e.g. amitraz;

(20) Mitochondrial complex III electron transport inhibitors e.g.

hydramethylnon, acequinocyl or fluacrypyrim;

(21) Mitochondrial complex I electron transport inhibitors e.g. METI

acaricides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben,

tebufenpyrad, tolfenpyrad or rotenone (Derris);

(22)Voltage-dependent sodium channel blockers e.g. indoxacarb or

metaflumizone;

(23) Inhibitors of acetyl CoA carboxylase e.g. Tetronic acid derivatives such

as spirodiclofen and spiromesifen; or tetramic acid derivatives such as

spirotetramat;

(24) Mitochondrial complex IV electron inhibitors e.g. Phosphines such as

aluminium phosphide, calcium phosphide, phosphine, and zinc phosphide

or cyanide;

(25) Mitochondrial complex II electron transport inhibitors e.g. Cyenopyrafen;

(28) Ryanodine receptor modulators e.g. diamides such as flubendiamide,

chlorantraniliprole (Rynaxypyr), cyantraniliprole (Cyazypyr), 3-bromo-N-

{2-bromo-4-chloro-6- [(1-cyclopropylethyl) carbamoyl]phenyl }-1-(3 -

chloropyridin-2-yl)-lH-pyrazole-5-carboxamide and methyl 2-[3,5-

dibromo-2-({[3-bromo-l-(3-chloropyridin-2-0-lH-pyrazol-5-

yl]carbonyl }amino)benzoyl] -1,2-dimethylhydrazinecarboxylate;

(29) azadirachtin, amidoflumet, benzoximate, bifenazate, chinomethionat,

cryolite, cyflumetofen, dicofol, fluensulfone (5-chloro-2-[(3,4,4-

trifluorobut-3-en-l-yl)sulfonyl]-l,3-thiazole), flufenerim, pyridalyl, and

pyrifluquinazon ;

in synergistically effective amounts.

In a preferred embodiment the invention relates to pesticidal mixtures






panecarboxylate

and

2) one or more further active ingredients (II) selected from the group consisting

of

abamectin, acequinocyl, acephate, acetamiprid, acrinathrin, afidopyraben,

alanycarb, albendazole, aldicarb, allethrin, p -cypermethrin, aluminium

phosphide, amitraz, azadirachtin, azamethiphos, azinphos-ethyl, azocyclotin,

Bacillus firmus, Bacillus sphaericus, fi cz thuringiensis (including susp.),

bendiocarb, benfuracarb, bensultap, benzoximate, bephenium, betacyfluthrin,

beto-cypermethrin, bifenazate, bifenthrin, bioallethrin, bioallethrin S-

cyclopentenyl isomer, bioresmethrin, bistrifluron, borax, BPMC, brofenprox,

bromophos, bromopropylate, brotianide, bufencarb, buprofezin, butamisole,

butocarboxim, butoxycarboxim, butylpyridaben, cadusafos, calcium phosphide,

cambendazole, carbaryl, carbofuran, carbophenothion, carbosulfan, cartap

hydrochloride , chinomethionat, chloethocarb, chlorantraniliprole, chlordane,

chlorfenapyr, chloroethoxyfos, chlorofenvinphos, chlorofluazuron,

chloromephos, chloropicrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide,

cis-resmethrin, clocythrin, clofentezine, clorsulon, closantel, clothianidin,

cryolite, coumaphos, cyanide, cyantraniliprole, cyanophos, cyclaniliprole,

cycloprothrin, cyenopyrafen, cyflumetofen, cyfluthrin, cyhalothrin, cyhexatin,

cypermethrin, cyphenothrin, cyromazine, d-cis-trans allethrin, deltamethrin,

DDT, demeton-S-methyl, diafenthiuron, diamphenethide, dibromosalan,

dichlorophen, 1,3-dichloroprene, difenthiuron, diazinon, dichlofenthion,

dichlorvos, dicliphos, dicofol, dicrotophos, diethion, diethylcarbamazine,

diflovidazin, diflubenzuron, dimethoate, dimethyl disulphide, dimethylvinphos,

dinotefuran, dioxathion, disulfoton, DNOC, d-trans allethrin, edifenphos,

endosulfan, emamectin(-benzoate), empenthrin, EPN, epsiprantel, esfenvalerate,

ethiofencarb, ethion, ethiprole, ethofenprox, ethoprop, ethoprophos, etoxazole,

etrimphos, famphur, febantel, fenamiphos, fenbendazole, fenazaquin, fenbutatin

oxide, fenitrothion, fenobucarb, fenothiocarb, fenoxycarb, fenpropathrin,

fenpyrad, fenpyroximate, fenthion, fenvalerate, fipronil, flometoquin,

flonicamid, fluacrypyrim, fluazuron, flubendazole, flubendiamide,

flucycloxuron, flucythrinate, flufenoxuron, flufenprox, flufiprole, flumethrin,

fluopyram, fluvalinate, flupyradifurone, fonophos, formetanate, formothion,

fosthiazate, fubfenprox, furathiocarb, furfural, gamma-cyhalothrin, halfenprox,

halofenozide, haloxon, heptafluthrin, heptenophos, Heterorhabtlitis

bacteriophora, hexaflumuron, hexachlorophene, hexythiazox, hydramethylnon,

hydroprene, imicyafos, imidacloprid, imiprothrin, indoxacarb, iprobenfos,

isazophos, isofenfox, isofenphos, isoprocarb, isopropyl-O-salicylate, isoxathion,

ivermectin, kadethrin, kinoprene, lambda-cyhalothrin, lepimectin, levamisole,

lufenuron, malathion, mebendazole, mecarbam, mevinphos, mesulfenphos,

metaflumizone, metaldehyde, metam sodium, metam potassium, methacrifos,

methamidophos, methidathion, methiocarb, methomyl, methoxychlor,

methoxyfenozide, methyl bromide, methyridine, metolcarb, mevinphos,

milbemectin, momfluorothrin, monocrotophos, morantel, Myrothecium

verrucaria strains, naled, netobimin, niclopholan, niclosamide, nicotine,

nitenpyram, nitroxynil, novaluron, noviflumuron, omethoate, oxamyl,

oxfendazole, oxibendazole, oxyclozanide, oxydemethon-M, oxydeprofos,

parathion A, parathion M, parbendazol, Pasteuria spp., permethrin,

phenothiazine, phenothrin, phenthoate, phorate, phosalone, phosmet,

phosphorodithioate, phosphamidon, phosphine, phostebupirim, phoxim,

piperonyl butoxide, pirimicarb, pirimiphos-methyl, prallethrin, praziquantel,

profenofos, promecarb, propargite, propaphos, propetamphos, propoxur,

prothiofos, prothoate, pyflubumide, pymetrozine, pyrachlophos, pyrantel,

pyridalyl, pyridaphenthion, pyresmethrin, pyrethrum, pyridaben, pyrimidifen,

pyriproxyfen, quinalphos, rafoxanide, resmethrin, ronnel, rotenone,

dioxabenzophos (salithion), Saponins of Quillaja saponaria, sebufos,

silafluofen, spinosad, spinetoram, spirodiclofen, spiromesifen, spirotetratmat,

Steinernema scapterisci strains, Steinernema feltiae, Steninernema kraussei,

sulfotep, sulfoxaflor, sulfuramid, sulfuryl floride, sulprofos, tasmanone, tatar

emetic, taa-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,

tellubenzuron, tefluthrin, temephos, terbam, terbufos, tetradifon, tetra-

chlorvinphos, tetramethrin, tetramisole, thenium, i/zeta-cypermethrin,

thiabendazole, thiacloprid, thiafenox, thiamethoxam, thiocyclam, thiodicarb,

thiofanox, thiomethon, thionazin, thiophanate, thiosultap- sodium, thuringiensin,

tolfenpyrad, tralomethrin, transfluthrin, triarathen, triazamate, triazophos,

triazuron, trichlorfon, triclabendazole, triflumuron, trimethacarb, vamidothion,

XMC, xylylcarb, zeta-cypermethrin, zinc phosphide, Bacillus firmus, Bacillus

sphaericus, fi cz thuringiensis (including susp.), Heterorhabtlitis

bacteriophora, Myrothecium verrucaria strains, Pasteuria spp., Saponins of

Quillaja saponaria, Steinernema scapterisci strains, and Steinernema feltiae,

Steninernema kraussei;

in synergistically effective amounts.

Table 1: mixtures of particular interest:

I + aldicarb I + alanycarb I + nitenpyram I + thiaclopridI + benfuracarb I + carbaryl I + thiamethoxam I + spinosadI + butocarboxim I + butoxycarboxim I + spinetoram I + abamectinI + carbofuran I + carbosulfan I + emamectin benzo. I + ipimectinI + formetanate I + triazamate I + milbemectin I + lepimectinI + methiocarb I + methomyl I + kinoprene I + hydropreneI + oxamyl I + primicarb I + pyriproxyfen I + fenoxycarbI + propoxur I + thiodicarb I + fenbutatin oxide I + diafenthiuronI + acephate I + azamethiphos I + chlorfenapyr I + propargiteI + azinphos-ethyl I + azinphos-methyl I + diflubenzuron I + bistrifluronI + chlorfenvinphos I + chlorpyrifos I + hexaflumuron I + flufenoxuronI + chlorpyrifos-Me I + demeton-S-Me I + novaluron I + lufenuronI + coumaphos I + ethoprophos I + chlorfluazuron I + flucycloxuronI + diazinon I + dichlorvos I + noviflumuron I + triflumuronI + dicrotophos I + dimethoate I + penfluron I + teflubenzuronI + disulfoton I + ethion I + halofenozide I + methoxyfenozideI + EPN I + famphur I + azadirachtin I + tebufenozideI + imicyafos I + isopropyl-O-salic. I + tolfenpyrad I + pyridabenI + fenitrothion I + fenthion I + fanazaquin I + fenpyroximateI + isoxathion I + malathion I + tebufenpyrad I + pyrimidinI + methamidaphos I + methidathion I + indoxacarb I + flufenerimI + mevinphos I + monocrotophos I + spirodiclofen I + metaflumizoneI + oxymethoate I + oxydemeton-Me I + spirotetramat I + spiromesifenI + parathion I + parathion-Me I + amitraz I + amidoflumetI + phenthoate I + phorate I + clofentezine I + bifenazateI + phosalone I + phosmet I + cyflumetofen I + cyenopyrafenI + phosphamidon I + pirimiphos-Me I + flonicamid I + etoxazoleI + quinalphos I + terbufos I + flupyrazophos I + flubendiamineI + tetra-chlorvinphos I + triazophos I + piperonyl butoxide I + hexythiazoxI + trichlorfon I + acetoprole I + pyridalyl I + pymetrozineI + propetamphos I +chlordane I + chlorantraniliprole I + pyrifluquinazonI + ethiprole I + fipronil I + acequinocyl I + Al-phosphideI + pyrafluprole I + pyriprole I + benzoximate I + boraxI + vaniliprole I + allethrin I + calcium phosphide I + chinomethionateI + gamma-cyhalothrin I + cyfluthrin I + chloroethoxyfos I + cryoliteI + lambda-cyhalothrin I + cypermethrin I + cyantraniliprole I + cyclaniliproleI + alpha-cypermethrin I + beta-cypermethrin I + flufiprole I + flubendiamideI + zeta-cypermethrin I + deltamethrin I + DDT I + dicofolI + esfenvalerate I + etofenprox I + diflovidazin I +DNOCI + fenpropathrin I + fenvalerate I + furfural I + fluacrypyrimI + flucythrinate I + tau-fluvalinate I + hydramethylnon I + methoxychlorI + permethrin I + silafluofen I + methyl bromide I + phosphineI + bioallethrin I + d-cis-tra. allethrin I + rotenone I + dioxabenzofosI + d-trans allethrin I + resmethrin I + sulfoxaflor I + sulfuryl fluorideI + bioresmethrin I + cyphenothrin I + tetradifon I + flometoquinI + -cypermethrin I + flumethrin I + pyflubumide I + afidopyrabenI + empenthrin I + imiprothrin I + tasmanone I + flupyradifurone

I + halfenprox I + phenothrin I + tefluthrin I + Bacillussphaericus

I + kadethrin I + tetramethrin I + Bacillus firmus I + Heterorhabtlitisbacteriophora

I + prallethrin I + transfluthrin I + Bacillus I + Pasteuria spp.thuringiensis

I + heptafluthrin I + momfluorothrin I + Myrothecium I + Steinernemaverrucaria strains scapterisci strains

I + tralomethrin I + nicotine I + Saponins of I + SteninernemaQuillaja saponaria kraussei

I + cartap I + thiocyclam I + dinotefuran I + Steinernemafeltiae

I + acetamiprid I + chlothianidin I + imidacloprid I + chloropicriniI + chlorethoxyfos I + ethoprop I + isofenfox I + temephosI + naled I + oxydeprofos I + phostebupirim I + phoximI + profenofos I + ronnel

More preferred are the combinations of the compound (I) with one or more

compounds selected among: Organophosphates such as acephate, azamethiphos,

azinphos (-methyl, -ethyl), cadusafos, chlorethoxyfos, chlorfenvinphos,

chlorfenvinphos, chlormephos, chlorpyrifos (-methyl), coumaphos, cyanophos,

demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate,

dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos,

fenitrothion, fenthion, fosthiazate, heptenophos, isofenphos, isopropyl O-

(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam,

methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate,

oxydemeton-methyl, parathion (-methyl), phenthoate, phorate, phosalone,

phosmet, phosphamidon, phoxim, pirimiphos (-methyl), profenofos,

propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep,

tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos,

triclorfon, and vamidothion - and especially selected among chlorpyrifos,

chlorpyrifos-methyl, dimethoate or malathion; Phenylpyrazoles such as

ethiprole, fipronil, pyrafluprole, and pyriprole - and especially fipronil or

ethiprole; Pyrethroids such as acrinathrin, allethrin (d-cis-trans, d-trans),

bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl, bioresmethrin,

cycloprothrin, cyfluthrin (beta-), cyhalothrin (gamma-, lambda-), cypermethrin

(alpha-, beta-, theta-, zeta-), cyphenothrin [(lR)-trans-isomers], deltamethrin,

dimefluthrin, empenthrin [(EZ)-(lR)-isomers), esfenvalerate, etofenprox,

fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (tau-),

halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin [(lR)-trans-

isomer), prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen,

tefluthrin, tetramethrin [(lR)-isomers)], tralomethrin, transfluthrin - and

especially selected among bifenthrin, deltamethrin, lambda-cyhalothrin, gamma-

cyhalothrin and tefluthrin; Chloronicotinyls such as acetamiprid, clothianidin,

dinotefuran, imidacloprid, nitenpyram, thiacloprid, thiamethoxam - and

especially selected among acetamiprid, imidacloprid, thiacloprid and

thiamethoxam; Avermectins such as abamectin, aversectin C, doramectin,

emamectin(-benzoate), eprinomectin, ivermectin, lepimectin and selamectin -

especially selected among abamectin and emmamectin-benzoate;

Diacylhydrazines such as chromafenozide, halofenozide, methoxyfenozide, and

tebufenozide - and especially methoxyfenozide; Spinosyns - especially selected

among spinosad and spinetoram; Juvenile hormone mimics such as hydroprene,

kinoprene, methoprene, fenoxycarb or pyriproxyfen - and especially

pyriproxyfen; Benzoylureas especially selected among bistrifluron,

chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron,

lufenuron, novaluron, noviflumuron, penfluron, teflubenzuron and triflumuron -

especially selected among lufenuron and novaluron; and Ryanodine receptor

modulators especially selected among flubendiamide, chlorantraniliprole and

cyantraniliprole.

The present invention also provides methods and uses for the control of insects,

arachnids or nematodes comprising the exposure of the insect, arachnid, or

nematode or their food supply, habitat, breeding grounds or their locus with a

pesticidally effective amount of mixtures of the active compound I with at least

one active compound II.

The mixtures of the active compounds I and II, or the active compounds I and II

used simultaneously, that is jointly or separately, exhibit outstanding action

against pests from the following orders:

Insects from the order of the lepidopterans (Lepidoptera), for example Agrotis

ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis,

Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia

murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana,

Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus

pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus

lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria

mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera,

Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria,

Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb-

dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,

LithocoUetis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria

dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra

brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea,

Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea

operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella

xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula

absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugiperda,

Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix

viridana, Trichoplusia ni and Zeiraphera canadensis, beetles (Coleoptera), for

example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus

solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum,

Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blasto-

phagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum,

Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata,

Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema

tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica

longicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabrotica

speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis,

Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera

postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa

decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus

communis, Meligethes aeneus, Melolontha hippocastani, Melolontha

melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus,

Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga

sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia

japonica, Sitona lineatus and Sitophilus granaria, flies, mosquitoes (Diptera),

e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens,

Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles

gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus,

Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya

bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis,

Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia

sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex

nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta

melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique,

Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia

canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina

morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides,

Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura,

Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii,

Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia

titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina

stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami,

Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes,

Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum,

Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis,

Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus,

Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and

Tipula paludosa thrips (Thysanoptera), e.g. Dichromothrips corbetti,

Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella

tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites

(Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes

aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes

lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis,

and Coptotermes formosanus, cockroaches (Blattaria-Blattodea), e.g. Blattella

germanica, Blattella asahinae, Periplaneta americana, Periplaneta japonica,

Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta

orientalis, bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas

(Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus,

Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps,

Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus

pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor,

Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae,

Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis

schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum,

Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus

helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne

brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,

Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphis

radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri,

Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae, Macrosiphum

avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae,

Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae, Myzus

ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri, Nilaparvata

lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla

mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis,

Rhopalosiphum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis

mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae,

Trialeurodes vaporariorum, Toxoptera aurantiiand, Viteus vitifolii, Cimex

lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., and Arilus

critatus. ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta

cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta

sexdens, Atta texana, Crematogaster spp., Hoplocampa minuta, Hoplocampa

testudinea, Lasius niger, Monomorium pharaonis, Solenopsis geminata,

Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex

barbatus, Pogonomyrmex californicus, Pheidole megacephala, Dasymutilla

occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris,

Paravespula pennsylvanica, Paravespula germanica, Dolichovespula maculata,

Vespa crabro, Polistes rubiginosa, Camponotus floridanus, and Linepithema

humile, crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,

Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus

femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus

spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca

gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus

senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria

angulifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana

pardalina, arachnoidea, such as arachnids (Acarina), e.g. of the families

Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,

Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus

annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum,

Dermacentor andersoni, Dermacentor variabilis, Hyalomma truncatum, Ixodes

ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes

pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata,

Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis,

Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi,

Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyl-

locoptrata oleivora and Eriophyes sheldoni; Tarsonemidae spp. such as

Phytonemus pallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such

as Brevipalpus phoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus,

Tetranychus kan- zawai, Tetranychus pacificus, Tetranychus telarius and

Tetranychus urticae, Panonychus ulmi, Panonychus cirri, and Oligonychus

pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa, fleas

(Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla

cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus, silverfish,

firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica,

centipedes (Chilopoda), e.g. Scutigera coleoptrata, millipedes (Diplopoda), e.g.

Narceus spp., earwigs (Dermaptera), e.g. forficula auricularia, lice

(Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis,

Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus

vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and

Solenopotes capillatus. Plant parasitic nematodes such as root-knot nematodes,

Meloidogyne arenaria, Meloidogyne chitwoodi, Meloidogyne exigua,

Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica and other

Meloidogyne species; cyst nematodes, Globodera rostochiensis, Globodera

pallida, Globodera tabacum and other Globodera species, Heterodera avenae,

Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other

Heterodera species; seed gall nematodes, Anguina funesta, Anguina tritici and

other Anguina species; stem and foliar nematodes, Aphelenchoides besseyi,

Aphelenchoides fragariae, Aphelenchoides ritzemabosi and other

Aphelenchoides species; sting nematodes, Belonolaimus longicaudatus and

other Belonolaimus species; pine nematodes, Bursaphelenchus xylophilus and

other Bursaphelenchus species; ring nematodes, Criconema species,

Criconemella species, Criconemoides species, and Mesocriconema species; stem

and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci, Ditylenchus

myceliophagus and other Ditylenchus species; awl nematodes, Dolichodorus

species; spiral nematodes, Helicotylenchus dihystera, Helicotylenchus

multicinctus and other Helicotylenchus species, Rotylenchus robustus and other

Rotylenchus species; sheath nematodes, Hemicycliophora species and

Hemicriconemoides species; Hirshmanniella species; lance nematodes,

Hoplolaimus columbus, Hoplolaimus galeatus and other Hoplolaimus species;

false root-knot nematodes, Nacobbus aberrans and other Nacobbus species;

needle nematodes, Longidorus elongates and other Longidorus species; pin

nematodes, Paratylenchus species; lesion nematodes, Pratylenchus brachyurus,

Pratylenchus coffeae, Pratylenchus curvitatus, Pratylenchus goodeyi,

Pratylencus neglectus, Pratylenchus penetrans, Pratylenchus scribneri,

Pratylenchus vulnus, Pratylenchus zeae and other Pratylenchus species;

Radinaphelenchus cocophilus and other Radinaphelenchus species; burrowing

nematodes, Radopholus similis and other Radopholus species; reniform

nematodes, Rotylenchulus reniformis and other Rotylenchulus species;

Scutellonema species; stubby root nematodes, Trichodorus primitivus and other

Trichodorus species; Paratrichodorus minor and other Paratrichodorus species;

stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and

other Tylenchorhynchus species and Merlinius species; citrus nematodes,

Tylenchulus semipenetrans and other Tylenchulus species; dagger nematodes,

Xiphinema americanum, Xiphinema index, Xiphinema diversicaudatum and

other Xiphinema species; and other plant parasitic nematode species.

The mixtures of the present invention are also suitable for being used for

controlling harmful pests (e.g. parasites) in and on animals, especially for

controlling ecto-parasites on animals.

An object of the present invention is therefore also to provide new methods to

control harmful parasites in and on animals. Another object of the invention is to

provide safer pesticides for animals. Another object of the invention is further to

provide pesticides for animals that may be used in lower doses than existing

pesticides. Yet another object of the invention is to provide pesticides for

animals, which provide a long residual control of the parasites.

The invention also relates to compositions containing a pesticidal effective

amount of a compound (I) in mixture with one or more compound (II) in

combination with an acceptable carrier, for controlling pests, such as parasites,

in and on animals.

The present invention also provides a method for treating, controlling,

preventing and protecting animals against infestation and infection by harmful

pests including parasites, which comprises orally, topically or parenterally

administering or applying to the animals a parasiticidally effective amount of

mixture of the present invention or a composition comprising it.

The present invention also relates to the use of a mixture of the present

invention or a composition comprising it for treating, controlling, preventing

and protecting animals against infestation and infection by harmful pests

including parasites, said use comprise administering or applying a parasiticidally

effective amount of said mixture orally, topically or parenterally to the animals.

The invention also provides a process for the preparation of a composition for

treating, controlling, preventing or protecting animals against infestation or

infection by harmful pests, such as parasites, which comprises a pesticidal

effective amount of a mixture of the present invention or a composition

comprising it.

Activity of compounds against agricultural pests does not suggest their

suitability for control of endo- and ectoparasites in and on animals which

requires, for example, low, non-emetic dosages in the case of oral application,

metabolic compatibility with the animal, low toxicity, and a safe handling.

Surprisingly it has now been found that mixtures of the present invention are

suitable for controlling endo- and ecto-parasites in and on animals, and,

especially for controlling ecto-parasites on animals.

Mixtures of the present invention and compositions comprising them are

preferably used for controlling and preventing infestations and infections in

animals including warmblooded animals (including humans) and fish. They are

for example suitable for controlling and preventing infestations and infections in

mammals such as cattle, sheep, swine, camels, deer, horses, pigs, rabbits, goats,

dogs and cats, water buffalo, donkeys, fallow deer and reindeer and also in fur-

bearing animals such as mink, chinchilla and raccoon; birds and poultry such as

hens, geese, turkeys and ducks; and fish such as fresh- and salt-water fish such

as trout, carp and eels.

Mixtures of the present invention and compositions comprising them are

preferably used for controlling and preventing infestations and infections in

domestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are not limited to,

lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic

fly larvae, chiggers, gnats, mosquitoes and fleas.

The mixtures of the present invention and compositions comprising them are

suitable for systemic and/or non-systemic control of ecto- and/or endoparasites.

They are active against all or some stages of development.

The mixture of the present invention is especially useful for controlling parasites

of the following orders and species, respectively:

Fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,

Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus;

cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae,

Pe-riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta

fuligginosa, Periplaneta australasiae, and Blatta orientalis; flies, mosquitoes

(Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha

ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus,

Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles

minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana,

Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops

silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia

anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex

quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura,

Dermatobia hominis, Fannia canicularis, Gasterophilus intestinalis, Glossina

morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides,

Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma

lineata, Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata,

Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans,

Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora

discolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophaga sp.,

Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus,

Tabanus lineola, and Tabanus similis; lice (Phthiraptera), e.g. Pediculus

humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus

eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon

gallinae, Menacanthus stramineus and Solenopotes capillatus; ticks and parasitic

mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus,

Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni,

Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum,

Ornithodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata),

e.g. Omithonyssus bacoti, Dermanyssus gallinae, Actinedida (Prostigmata) and

Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia

spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,

Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes

spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes

spp., Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptes

spp; bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius

senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus;

Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus

spp., and Solenopotes spp.; Mallophagida (suborders Arnblycerina and

Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola

spp., Werneckiella spp., Lepikentron spp., Trichodectes spp., and Felicola spp;

roundworms Nematoda: Wipeworms and Trichinosis (Trichosyringida), e.g.

Trichinellidae (Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp.;

Pvhabditida, e.g. Rhabditis spp., Strongyloides spp., Helicephalobus spp.;

Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus,

Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus.,

Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp.,

Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanus

spp., Chabertia spp., Stephanurus dentatus, Syngamus trachea, Ancylostoma

spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp.,

Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp.,

Parelaphostrongylus spp., Aleuro strongylus abstrusus, and Dioctophyma renale;

Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum,

Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm),

Toxocara canis, Toxascaris leonine, Skrjabinema spp. and Oxyuris equi;

Camallanida, e.g. Dracunculus medinensis (guinea worm); Spirurida, e.g.

Thelazia spp., Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp.,

Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi and

Habronema spp.; Thorny headed worms (Acanthocephala), e.g.

Acanthocephalus spp., Macracanthorhynchus hirudinaceus and Oncicola spp;

Planarians (Plathelminthes): Flukes (Trematoda), e.g. Faciola spp., Fascioloides

magna, Paragonimus spp., Dicrocoelium spp., Fasciolopsis buski, Clonorchis

sinensis, Schistosoma spp., Trichobilharzia spp., Alaria alata, Paragonimus spp.,

and Nanocyetes spp.; Cercomeromorpha, in particular Cestoda (Tapeworms),

e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium

caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis

spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp.,

and Hymenolepis spp..

In a second aspect of the invention, there are provided pesticidal mixtures






5 panecarboxylate

and

least one fungicidal compound (II) selected from the following

10 II. 1) methyl benzimidazole carbamate (MBC) fungicides;

II.2) dicarboximide fungicides;

II.3) demethylation inhibitor (DMI) fungicides;

II.4) phenylamide fungicides;

II.5) amine/morpholine fungicides;

15 II.6) phospholipid biosynthesis inhibitor fungicides;

II.7) carboxamide fungicides;

II.8) hydroxy (2-amino -)pyrimidine fungicides ;

II.9) anilinopyrimidine fungicides;

11.10) N-phenyl carbamate fungicides;

20 11.11) quinone outside inhibitor (Qol) fungicides;

11.12) phenylpyrrole fungicides;

11.13) quinoline fungicides;

11.14) lipid peroxidation inhibitor fungicides;

11.15) melanin biosynthesis inhibitors-reductase (MBI-R) fungicides;

25 11.16) melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides;

11.17) hydroxy anilide fungicides;

11.18) squalene-epoxidase inhibitor fungicides;

11.19) polyoxin fungicides;

11.20) phenylurea fungicides;

30 11.21) quinone inside inhibitor (Qil) fungicides;

11.22) benzamide fungicides;

enopyranuronic acid antibiotic fungicides;

hexopyranosyl antibiotic fungicides;

glucopyranosyl antibiotic: protein synthesis fungicides;

glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides;

cyanoacetamideoxime fungicides;

carbamate fungicides;

oxidative phosphorylation uncoupling fungicides;

organo tin fungicides;

carboxylic acid fungicides;

heteroaromatic fungicides;

phosphonate fungicides;

phthalamic acid fungicides;

benzotriazine fungicides;

benzene-sulfonamide fungicides;

pyridazinone fungicides;

thiophene-carboxamide fungicides;

pyrimidinamide fungicides;

carboxylic acid amide (CAA) fungicides;

tetracycline antibiotic fungicides;

thiocarbamate fungicides;

benzamide fungicides;

host plant defense induction fungicides;

multi-site contact activity fungicides;

in a synergistically effective amount.

In particular the at least one fungicidal compound (II) is selected from the

following groups:

A) azoles, in particular: azaconazole, bitertanol, bromuconazole, cyproconazole,

difenoconazole, diniconazole, enilconazole, epoxiconazole, flutriafol,

fluquinconazole, fenbuconazole, flusilazole, hexaconazole, imibenconazole,

ipconazole, metconazole, myclobutanil, oxpoconazole, penconazole,

propiconazole, prothioconazole, pyrisoxazole, simeconazole, triadimefon,

triadimenol, tebuconazole, tetraconazole, triticonazole, prochloraz, pefurazoate,

imazalil, triflumizole, cyazofamid, benomyl, carbendazim, thiabendazole,

fuberidazole, ethaboxam, etridiazole, hymexazole;

B) strobilurins, in particular: azoxystrobin, coumoxystrobin, enoxastrobin,

dimoxystrobin, fenaminstrobin, enestroburin, fluoxastrobin, kresoxim-methyl,

metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin,

pyrametostrobin, triclopyricarb, pyraoxystrobin, fenamidone, famoxadone, or

pyribencarb;

C) carboxamides, in particular: carboxin, benalaxyl, benodanil, boscalid,

fenfuram, fenhexamid, fenpyrazamine, flutolanil, furalaxyl, furametpyr,

isofetamid, isotranil, kiralaxyl, mepronil, metalaxyl, mefenoxam, ofurace,

oxadixyl, oxycarboxin, penthiopyrad, pyrimorph, thifluzamide, tiadinil, bixafen,

dimethomorph, flumorph, flumetover, fluopicolide (picobenzamid), zoxamide,

carpropamid, diclocymet, mandipropamid, isopyrazam, fluxapyroxad, sedaxane,

penflufen, fluopyram;

D) heterocylic compounds, in particular: fluazinam, pyrifenox, bupirimate,

cyprodinil, fenarimol, ferimzone, mepanipyrim, nuarimol, pyrimethanil,

triforine, fenpiclonil, fludioxonil, aldimorph, chloozolinate, dimethirimol,

dodemorph, ethirimol, fenpropimorph, tridemorph, fenpropidin, iprodione,

piperalin. procymidone, vinclozolin, famoxadone, fenamidone, octhilinone,

probenazole, pyrisoxazole, amisulbrom, anilazine, diclomezine, pyroquilon,

proquinazid, tricyclazole, acibenzolar-S-methyl, captafol, captan, dazomet,

folpet, fenoxanil, quinoxyfen;

E) carbamates, in particular: mancozeb, maneb, metam, metiram, ferbam,

propineb, thiram, zineb, ziram, benthiavalicarb, diethofencarb, iodocarb,

iprovalicarb, flubenthiavalicarb, methasulfocarb, propamocarb, prothiocarb,

pyributicarb, valifenalate; and

F) other active compounds, selected from guanidines: dodine, iminoctadine and

guazatine; antibiotics: blasticidin-S, kasugamycin, streptomycin,

oxytetracycline, polyoxin and validamycin; nitrophenyl derivates: binapacryl,

dinocap, dinobuton and meptyldinocap; sulfur-containing heterocyclyl

compounds: dithianon and isoprothiolane; organometal compounds: fentin salts,

such as fentin-acetate, chloride or hydroxide; organophosphorus compounds:

edifenphos, iprobenfos, fosetyl, fosetyl-AL, phosphorous acid and its salts,

pyrazophos and tolclofos-methyl; organochlorine compounds: biphenyl,

chloroneb, dicloran, chlorothalonil, dichlofluanid, flusulfamide,

hexachlorobenzene, phthalide, pencycuron, quintozene, tecnazene, thiophanate-

methyl and tolylfluanid; inorganic active compounds: Bordeaux mixture, copper

acetate, copper hydroxide, copper oxychloride, basic copper sulfate and sulfur;

others: cyflufenamid, cymoxanil, dimethirimol, ethirimol, furalaxyl,

metrafenone, flutianil, pyriofenone, bupirimate and spiroxamine; Bacillus

spp.: B. subtilis and B amyloliquefaciens; plant extracts: Melaleuca alternifolia;

in a synergistically effective amount.

The synergistic effect provided is both in respect of insecticidal, acaricidal,

nematicidal effect and fungicidal effect.

Table 2 : Mixtures of particular interest:

I + bitertanol I + bromuconazole I + isopyrazam I + fluxapyroxadI + cyproconazole I + difenoconazole I + sedaxane I + penflufenI + diniconazole I + enilconazole I + flumetover I + penflufenI + epoxiconazole I + fluquinconazole I + fluopyram I + benzovindiflupyrI + fenbuconazole I + flusilazole I + fluazinam I + pyrifenoxI + flutriafol I + hexaconazole I + cyprodinil I + fenarimolI + imibenconazole I + ipconazole I + ferimzone I + mepanipyrimI + metconazole I + myclobutanil I + nuarimol I + pyrimethanilI + penconazole I + propiconazole I + triforine I + fenpiclonilI + prothioconazole I + simeconazole I + fludioxonil I + aldimorphI + oxpoconazole I + pyrisoxazole I + dodemorph I + fenpropimorphI + triadimefon I + triadimenol I + tridemorph I + fenpropidinI + tebuconazole I + tetraconazole I + iprodione I + procymidoneI + triticonazole I + prochloraz I + vinclozolin; I + famoxadoneI + pefurazoate I + imazalil I + fenamidone I + octhilinoneI + triflumizole I + cyazofamid I + probenazole; I + amisulbromI + benomyl I + carbendazim I + anilazine I + diclomezineI + thiabendazole I + fuberidazole I + pyroquilon I + proquinazidI + ethaboxam I + etridiazole I + tricyclazole I + acibenzolar-S-MeI + hymexazole I + azoxystrobin I + captafol I + captanI + dimoxystrobin I + enestroburin I + dazomet I + folpet

I + fluoxastrobin I + kresoxim-methyl I + fenoxanil I + quinoxyfenI + metominostrobin I + orysastrobin I + bupirimate I + chloozolinateI + picoxystrobin I + pyraclostrobin I + dimethirimol I + ethirimolI + benzothiostrobin I + coumethoxystrobin I + piperalin I + pyrisoxazoleI + coumoxystrobin I + enoxastrobin I + mancozeb I + manebI + fenaminstrobin I + flufenoxystrobin I + metam I + metiramI + mandestrobin I + pyrametostrobin I + ferbam I + propinebI + pyriministrobin I + triclopyricarb I + thiram I + zinebI + pyraoxystrobin I + fenamidone I + ziram I + diethofencarbI + famoxadone I + pyribencarb I + iprovalicarb I + flubenthiavalicarbI + trifloxystrobin I + carboxin I + benthiavalicarb I + iodocarbI + benalaxyl I + boscalid I + methasulfocarb I + prothiocarbI + fenhexamid I + flutolanil I + pyributicarb I + valifenalateI + furametpyr I + mepronil I + Propamocarb I + dodineI + metalaxyl I + mefenoxam I + iminoctadine I + benthiavalicarbI + ofurace I + oxadixyl I + streptomycin I + polyoxineI + oxycarboxin I + penthiopyrad I + binapacryl I + dinocapI + thifluzamide I + tiadinil I + dinobuton I + dithianonI + dimethomorph I + flumorph I + isoprothiolane I + fentin-acetateI + fluopicolid I + zoxamide I + edifenphos I + iprobenfosI + diclocymet I + mandipropamid I + fosetyl I + fosetyl-aluminumI + benodanil I + fenfuram I + phosphorous acid I + pyrazophosI + fenpyrazamine I + furalaxyl I + tolclofos-methyl I + chlorothalonilI + isofetamid I + isotranil I + dichlofluanid I + flusulfamideI + kiralaxyl I + pyrimorph I + hexachlorobenzene I + phthalideI + bixafen I + carpropamid I + pencycuron I + quintozeneI + guazatine I + blasticidin-S I + thiophanate-methyl I + tolylfluanidI + kasugamycin I + oxytetracycline I + Bordeaux mixture I + copper acetateI + validamycin I + meptyldinocap I + copper hydroxide I + Cu-oxychlorideI + biphenyl I + chloroneb I + copper sulfate I + cyflufenamidI + dicloran I + chlorothalonil I + cymoxanil I + dimethirimolI + dichlofluanid I + flusulfamide I + ethirimol I + flutianilI + tecnazene I + pyriofenone I + metrafenone I + spiroxamineI + bupirimate I + oxathiapiprolin

The mixtures of a compound (I) and a compound (II) or the simultaneous, that is

joint or separate, use of a compound (I) and a compound (II) are distinguished

by being highly active against a wide range of phytopathogenic fungi, in

particular from the classes of the Ascomycetes, Deuteromycetes,

Peronosporomycetes and Basidiomycetes. The mixtures act systemically,

translaminar or through contact and can be used in crop protection as foliar

fungicides, as fungicides for seed dressing and as soil-acting fungicides.

Advantageously, the mixtures comprising one or more fungicides are suitable

for controlling the following plant diseases:

Albugo spp. (white rust) on ornamentals, vegetables (e.g. A. Candida) and

sunflowers (e.g. A. tragopogonis), Alternaria spp. (Alternaria leaf spot) on

vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice,

soybeans, potatoes (e.g. A. solani or A. alternata), tomatoes (e.g. A. solani or A.

alternata) and wheat, Aphanomyces spp. on sugar beets and vegetables,

Ascochyta species on cereals and vegetables, e.g. A. tritici (anthracnose) on

wheat and A. hordei on barley, Bipolaris and Drechslera spp. (Teleomorph:

Cochliobolus spp.) on corn (e.g. D. maydis), cereals (e.g. B. sorokiniana: spot

blotch), rice (e.g. B. oryzae) and turfs, Blumeria (formerly Erysiphe) graminis

(powdery mildew) on cereals (e.g. on wheat or barley), Botrytis cinerea

(teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g.

strawberries), vegetables (e.g. lettuce, carrots, celery and cabbages), rape,

flowers, vines, forestry plants and wheat, Bremia lactucae (downy mildew) on

lettuce, Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad-leaved trees

and evergreens, e.g. C. ulmi (Dutch elm disease) on elms, Cercospora spp.

(Cercospora leaf spots) on corn, rice, sugar beets (e. g . C. beticola), sugar cane,

vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchii) and rice,

Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C.

herba-rum (black ear) on wheat, Claviceps purpurea (ergot) on cereals,

Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on

corn (C. carbonum), cereals (e.g. C. sativus, anamorph: B. sorokiniana) and rice

(e.g. C. miy- abeanus, anamorph: H. oryzae), Colletotrichum (teleomorph:

Glomerella) spp. (anthracnose) on cotton (e.g. C. gossypii), corn (e.g. C.

graminicola), soft fruits, potatoes (e.g. C. coccodes: black dot), beans (e.g. C.

lindemuthianum) and soybeans (e.g. C. truncatum), Corticium spp., e.g. C.

sasakii (sheath blight) on rice, Corynespora cassiicola (leaf spots) on soybeans

and ornamentals, Cycloconium spp., e.g. C. oleaginum on olive trees,

Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph:

Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph:

Neonectria liriodendri: Black Foot Disease) and ornamentals, Dematophora

(teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans, Diaporthe

spp., e.g. D. phaseolorum (damping off) on soybeans, Drechslera (syn.

Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as

barley (e.g. D. teres, net blotch) and wheat (e.g. D. tritici-repentis: tan spot), rice

and turf, Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn.

Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier

Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or

Botryosphaeria obtusa, Elsinoe spp. on pome fruits (E. pyri), soft fruits (E.

veneta: anthracnose) and vines (E. ampelina: anthracnose), Entyloma oryzae

(leaf smut) on rice, Epicoccum spp. (black mold) on wheat, Erysiphe spp.

(powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pisi), such as

cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. cruciferarum), Eutypa

lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella

blepharis) on fruit trees, vines and ornamental woods, Exserohilum (syn.

Helminthosporium) spp. on corn (e.g. E. turcicum), Fusarium (teleomorph:

Gibberella) spp. (wilt, root or stem rot) on various plants, such as F.

graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g.

wheat or barley), F. oxysporum on tomatoes, F. solani on soybeans and F.

verticillioides on corn, Gaeumannomyces graminis (take-all) on cereals (e.g.

wheat or barley) and corn, Gibberella spp. on cereals (e.g. G. zeae) and rice (e.g.

G. fujikuroi: Bakanae disease), Glomerella cingulata on vines, pome fruits and

other plants and G. gossypii on cotton, Grainstaining complex on rice,

Guignardia bidwellii (black rot) on vines, Gymnosporangium spp. on rosaceous

plants and junipers, e.g. G. sabinae (rust) on pears, Helminthosporium spp. (syn.

Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice, Hemileia spp.,

e.g. Hemileia vastatrix (coffee leaf rust) on coffee, lsariopsis clavispora (syn.

Cladosporium vitis) on vines, Macrophomina phaseolina (syn. phaseoli) (root

and stem rot) on soybeans and cotton, Microdochium (syn. Fusarium) nivale

(pink snow mold) on cereals (e.g. wheat or barley), Micro sphaera diffusa

(powdery mildew) on soybeans, Monilinia spp., e.g. M. laxa, M. fructicola and

M. fructigena (bloom and twig blight, brown rot) on stone fruits and other

rosaceous plants, Mycosphaerella spp. on cereals, bananas, soft fruits and

ground nuts, such as e.g. M. graminicola (anamorph: Septoria tritici, Septoria

blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas,

Peronospora spp. (downy mildew) on cabbage (e.g. P. brassicae), rape (e.g. P.

parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g.

P. manshurica), Phakopsora pachyrhizi and P. meibomiae (soybean rust) on

soybeans, Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora)

and soybeans (e.g. P. gregata: stem rot), Phoma lingam (root and stem rot) on

rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar

beets, Phomopsis spp. on sunflowers, vines (e. g . P. viticola: can and leaf spot)

and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum),

Physorma maydis (brown spots) on corn, Phytophthora spp. (wilt, root, leaf,

fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P.

capsici), soybeans (e.g. P. megasperma, syn. P. sojae), potatoes and tomatoes

(e.g. P. infestans: late blight) and broad-leaved trees (e.g. P. ramorum: sudden

oak death), Plasmodiophora brassicae (club root) on cabbage, rape, radish and

other plants, Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on

vines and P. halstedii on sunflowers, Podosphaera spp. (powdery mildew) on

rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples,

Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar

beets (P. betae) and thereby transmitted viral diseases, Pseudocercosporella

herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e.g. wheat

or barley, Pseudoperonospora (downy mildew) on various plants, e.g. P.

cubensis on cucurbits or P. humili on hop, Pseudopezicula tracheiphila (red fire

disease or rotbrenner', anamorph: Phialophora) on vines, Puccinia spp. (rusts) on

various plants, e.g. P. triticina (brown or leaf rust), P. striiformis (stripe or

yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P.

recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, and

asparagus (e. g . P. asparagi), Pyrenophora (anamorph: Drechslera) tritici-

repentis (tan spot) on wheat or P. teres (net blotch) on barley, Pyricularia spp.,

e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea

on turf and cereals, Pythium spp. (damping-off) on turf, rice, corn, wheat,

cotton, rape, sunflowers, sugar beets, vegetables and various other plants (e.g. P.

ultimum or P. aphanidermatum), Ramularia spp., e.g. R. collocygni (Ramularia

leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets,

Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets,

vegetables and various other plants, e.g. R. solani (root and stem rot) on

soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring

blight) on wheat or barley, Rhizopus stolonifer (black mold, soft rot) on

strawberries, carrots, cabbage, vines and tomatoes, Rhynchosporium secalis

(scald) on barley, rye and triticale, Sarocladium oryzae and S. attenuatum

(sheath rot) on rice, Sclerotinia spp. (stem rot or white mold) on vegetables and

field crops, such as rape, sunflowers (e.g. S. sclerotiorum) and soybeans (e.g. S.

rolfsii), Septoria spp. on various plants, e.g. S. glycines (brown spot) on

soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora)

nodorum (Stagonospora blotch) on cereals, Uncinula (syn. Erysiphe) necator

(powdery mildew, anamorph: Oidium tuckeri) on vines, Setospaeria spp. (leaf

blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf,

Sphacelotheca spp. (smut) on corn, (e.g. S. reiliana: head smut), sorghum und

sugar cane, Sphaerotheca fuliginea (powdery mildew) on cucurbits,

Spongospora subterranea (powdery scab) on potatoes and thereby transmitted

viral diseases, Stagonospora spp. on cereals, e.g. S. nodorum (Stagonospora

blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum) on wheat,

Synchytrium endobioticum on potatoes (potato wart disease), Taphrina spp., e.g.

T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on

plums, Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables,

soybeans and cotton, e.g. T. basicola (syn. Chalara elegans), Tilletia spp.

(common bunt or stinking smut) on cereals, such as e.g. T. tritici (syn. T. caries,

wheat bunt) and T. controversa (dwarf bunt) on wheat, Typhula incarnata (grey

snow mold) on barley or wheat, Urocystis spp., e.g. U. occulta (stem smut) on

rye, Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus,

syn. U. phaseoli) and sugar beets (e.g. U. betae), Ustilago spp. (loose smut) on

cereals (e.g. U. nuda und U. avaenae), corn (e.g. U. maydis: corn smut) and

sugar cane, Venturia spp. (scab) on apples (e.g. V. inaequalis) and pears,

Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines,

soft fruits, vegetables and field crops, e.g. V. dahliae on strawberries, rape,

potatoes and tomatoes.

The mixtures of the compound (I) and active compounds (II), when compound

(II) scomprise a fungicide, are furthermore suitable for controlling harmful pests

in the protection of materials (for example wood, paper, paint dispersions, fibers

or fabrics) and in the protection of stored products. In the protection of wood,

particular attention is paid to the following harmful fungi: Ascomycetes, such as

Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma

spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.;

Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp.,

Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp.,

Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp.,

Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes, such as

Mucor spp., additionally in the protection of materials the following yeasts:

Candida spp. and Saccharomyces cerevisae.

The mixtures according to the present invention can be converted into the

customary formulations, for example solutions, emulsions, suspensions, dusts,

powders, pastes and granules. The use form depends on the particular intended

purpose; in each case, it should ensure a fine and even distribution of the

compounds according to the invention.

The formulations are prepared in a known manner. By example and in particular

for crop protection use, the formulations can be prepared by extending the active

compound with auxiliaries suitable for the formulation of agrochemicals, such

as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants,

preservatives, anti-foaming agents, anti-freezing agents, for seed treatment

formulation also optionally gelling agents.

Examples of suitable solvents are water, aromatic solvents (for example

Solvesso products, xylene), paraffins (for example mineral oil fractions),

alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for

example cyclohexanone, gamma-butyrolactone), pyrrolidones e.g. NMP

(N-methyl-pyrrolidone) and NOP (N-octyl-pyrrolidone), acetates (glycol

diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In

principle, solvent mixtures may also be used.

Suitable emulsifiers are nonionic, cationic and anionic emulsifiers (for example

polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal and ammonium

salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid,

dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates,

alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol

glycol ethers, furthermore condensates of sulfonated naphthalene and

naphthalene derivatives with formaldehyde, condensates of naphthalene or of

naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene

octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,

alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl

polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene

oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers,

ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol

esters, lignosulfite waste liquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayable solutions,

emulsions, pastes or oil dispersions are mineral oil fractions of medium to high

boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of

vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for

example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated

naphthalenes or their derivatives, methanol, ethanol, propanol, butanol,

cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example

dimethyl sulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and

bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based on silicon

or magnesium stearate.

A suitable preservative is e.g. dichlorophen.

An example of a gelling agent is carrageen (Satiagel).

Powders, materials for spreading and dustable products can be prepared by

mixing or concomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules and homogeneous

granules, can be prepared by binding the active compounds to solid carriers.

Examples of solid carriers are mineral earths such as silica gels, silicates, talc,

kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite,

diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide,

ground synthetic materials, fertilizers, such as, for example, ammonium sulfate,

ammonium phosphate, ammonium nitrate, ureas, and products of vegetable

origin, such as cereal meal, tree bark meal, wood meal and nutshell meal,

cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight, preferably

from 0.1 to 90% by weight, of the active compounds. In this case, the active

compounds are employed in a purity of from 90% to 100% by weight,

preferably 95% to 100% by weight (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-10 fold

leading to concentrations in the ready to use preparations of 0.01 to 60% by

weight active compounds by weight, preferably 0 .1 to 40% by weight.

The mixtures of the present invention can be used as such, in the form of their

formulations or the use forms prepared therefrom, for example in the form of

directly sprayable solutions, microcapsule suspensions, powders, suspensions or

dispersions, emulsions, oil dispersions, pastes, dustable products, materials for

spreading, or granules, by means of spraying, atomizing, dusting, spreading or

pouring. The use forms depend entirely on the intended purposes; they are

intended to ensure in each case the finest possible distribution of the active

compounds according to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes or

wettable powders (sprayable powders, oil dispersions) by adding water. To

prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved

in an oil or solvent, can be homogenized in water by means of a wetter,

tackifier, dispersant or emulsifier. However, it is also possible to prepare

concentrates composed of active substance, wetter, tackifier, dispersant or

emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable

for dilution with water.

The active compound concentrations in the ready-to-use preparations can be

varied within relatively wide ranges. In general, they are from 0.0001 to 10%,

preferably from 0.01 to 1 % per weight.

The active compounds may also be used successfully in the ultra-low-volume

process (ULV), it being possible to apply formulations comprising over 95% by

weight of active compound, or even to apply the active compound without

additives.

The following are examples of formulations:

1. Products for dilution. For seed treatment purposes, such products may be

applied to the seed diluted or undiluted.

A) Water-soluble concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 parts by weight

of water or a water-soluble solvent. As an alternative, wetters or other

auxiliaries are added. The active compound(s) dissolve(s) upon dilution with

water, whereby a formulation with 10 % (w/w) of active compound(s) is

obtained.

B) Dispersible concentrates (DC)


of cyclohexanone with addition of 10 parts by weight of a dispersant, for

example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby

a formulation with 20% (w/w) of active compound(s) is obtained.

C) Emulsifiable concentrates (EC)


of xylene with addition of calcium dodecylbenzenesulfonate and castor oil

ethoxylate (in each case 5 parts by weight). Dilution with water gives an

emulsion, whereby a formulation with 15% (w/w) of active compound(s) is

obtained.

D) Emulsions (EW, EO, ES)


of xylene with addition of calcium dodecylbenzenesulfonate and castor oil

ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30

parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax)

and made into a homogeneous emulsion. Dilution with water gives an emulsion,

whereby a formulation with 25% (w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s) are

comminuted with addition of 10 parts by weight of dispersants, wetters and 70

parts by weight of water or of an organic solvent to give a fine active

compound(s) suspension. Dilution with water gives a stable suspension of the

active compound(s), whereby a formulation with 20% (w/w) of active

compound(s) is obtained.

F) Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely with addition of

50 parts by weight of dispersants and wetters and made as water-dispersible or

water-soluble granules by means of technical appliances (for example extrusion,

spray tower, fluidized bed). Dilution with water gives a stable dispersion or

solution of the active compound(s), whereby a formulation with 50% (w/w) of

active compound(s) is obtained.

G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in a rotor-stator mill

with addition of 25 parts by weight of dispersants, wetters and silica gel.

Dilution with water gives a stable dispersion or solution of the active

compound(s), whereby a formulation with 75% (w/w) of active compound(s) is

obtained.

H) Gel-Formulation (GF) In an agitated ball mill, 20 parts by weight of the

active compound(s) are comminuted with addition of 10 parts by weight of

dispersants, 1 part by weight of gelling agent wetters and 70 parts by weight of

water or of an organic solvent to give a fine active compound) suspension.

Dilution with water gives a stable suspension of the active compound(s),

whereby a formulation with 20% (w/w) of active compound(s) is obtained.

2 . Products to be applied undiluted. For seed treatment purposes, such products

may be applied to the seed diluted or undiluted.

I) Dustable powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixed

intimately with 95 parts by weight of finely divided kaolin. This gives a dustable

product having 5% (w/w) of active compound(s).

J) Granules (GR, FG, GG, MG)

0.5 part by weight of the active compound(s) is ground finely and associated

with 95.5 parts by weight of carriers, whereby a formulation with 0.5% (w/w) of

active compound(s) is obtained. Current methods are extrusion, spray-drying or

the fluidized bed. This gives granules to be applied undiluted for foliar use.

K) ULV solutions (UL)


of an organic solvent, for example xylene. This gives a product having 10%

(w/w) of active compound(s), which is applied undiluted for foliar use.

L) Capsule supensions (CS)

28 parts of a combination of the compound(s), or of each of these compounds

separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene

diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture

is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a

defoamer and 51.6 parts of water until the desired particle size is achieved. To

this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is

added. The mixture is agitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener

and 3 parts of a dispersing agent. The capsule suspension formulation contains

28% of the active ingredients. The medium capsule diameter is 3-10 microns.

Various types of oils, wetters, adjuvants, herbicides, fungicides, inseticides,

nematicides, acaricides, other pesticides, and/or bactericides may be added to

the active ingredients, if appropriate just immediately prior to use (tank mix).

These agents usually are admixed with the agents according to the invention in a

weight ratio of 1:20 to 20: 1.

Emulsifiable concentrates:

Active ingredient(s): 1 to 99%, preferably 60 to 90%

Surfactant: 1 to 30%, preferably 1 to 20%

Solvent: 1 to 80%, preferably 1 to 35%

Dusts:

Active ingredient(s): 0.1 to 90%, preferably 1 to 80%

Solid carrier: 1 to 99.9%, preferably 15 to 90%

Suspension concentrates:


Water: 24 to 94%, preferably 30 to 88%


Suspo-emulsion



Solvent 1 to 80%, preferably 1 to 35%

Wettable powders:



Solid carrier: 1 to 95%, preferably 15 to 90%

Granulates:



Solid carrier: 1 to 95%, preferably 15 to 90%

Suspension composition for seed treatment:Active ingredient(s): 0.1 to 90%, preferably 1 to 80%Surfactant: 1 to 40%, preferably 1 to 20%Solvent: 1 to 90%, preferably 1 to 50%Colorants: 0 to 40%, preferably 1 to 20%Binder: 0 to 60%, preferably 1 to 40%

The compound (I) and one or more compound(s) (II) can be applied

simultaneously, that is jointly or separately, or in succession, the sequence, in

the case of separate application, generally not having any effect on the result of

the control measures.

The mixtures of the present invention are employed as such or in form of

compositions by treating the insects, arachnid, nematode, fungi or the plants

(including crops), plant propagation materials such as seeds, part of the plant

and/or plant organ that grow at a later point in time, water in which plants grow,

soil, surfaces, materials or rooms to be protected from insecticidal acaricidal,

nematicidal or insecticidal-/acaricidal-/nematicidal-fungicidal attack with an

insecticidally, acaricidal, nematicidal or insecticidal-/acaricidal-/nematicidal-

fungicidally effective amount of the active compounds. The application can be

carried out both before and after the infection of the plants, plant propagation

materials such as seeds, part of the plant and/or plant organ that grow at a later

point in time, water in which plants grow, soil, surfaces, materials or rooms by

the insects or harmful pests.

The term "plant propagation material" is to be understood to denote all the

generative parts of the plant such as seeds and vegetative plant material such as

cuttings and tubers (e. g . potatoes), which can be used for the multiplication of

the plant. This includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots,

sprouts and other parts of plants. Seedlings and young plants, which are to be

transplanted after germination or after emergence from soil, may also be

included. These plant propagation materials may be treated prophylactically

with a plant protection compound either at or before planting or transplanting.

For crop use, the compound (I) and the one or more compound(s) (II) are

usually applied in a weight ratio of from 1000:1 and 1:1000. In other

embodiments that weight ratio of (I) to (II) may be between 500:1 to 1:500, for

example between 100:1 to 1:100, for example between 1:50 to 50:1, for example

1:20 to 20:1, for example 1:10 to 10:1, for example 1:5 to 5:1. Other examples

of weight ratios of (I) to (II) include 1:1, 1:2, 1:3, 1:4, 2:1,

3:1, 4:1. The invention also provides pesticidal mixtures comprising a

combination of components (I) and (II) as mentioned above in a synergistically

effective amount, together with an agriculturally acceptable carrier, and

optionally a surfactant. Depending on the desired effect, the specific mixture

partner(s), pest to be controlled, crop to be protected and/or soil or weather

condition, the application rates of the mixtures according to the invention are

e.g. from 2 g/ha to 2000 g/ha, preferably from 5 to 1500 g/ha, in particular from

10 to 1000 g/ha.

In a preferred embodiment amounts applied of compound (I) and/or the at least

one compound (II) is lower than the normal dose rate required to achieve the

same effect/result had either of the actives been applied individually, i.e. the

synergistic effect of the combination result in a lower dose rate of either or both

(or more) compounds required to achieve the same or improve the effect.

The inventive mixtures and the compositions comprising them can be used for

protecting materials (e.g. technical materials) e.g. wooden materials such as

trees, board fences, sleepers, etc. and buildings such as houses, outhouses,

factories, but also construction materials, furniture, leathers, fibers, vinyl

articles, electric wires and cables etc. from ants and/or termites, and for

controlling pests e.g. ants, flies, spiders, mosquitoes and termites from doing

harm to crops or human being (e.g. when the pests invade into houses and public

facilities).

Methods to control infectious diseases transmitted by insects (e.g. malaria,

dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with the

inventive mixtures and their respective compositions also comprise treating

surfaces of huts and houses, air spraying and impregnation of curtains, tents,

clothing items, bed nets, tsetse-fly trap or the like, insecticidal compositions for

application to fibers, fabric, knitgoods, non-wovens, netting material or foils and

tarpaulins preferably comprise a composition including the inventive mixtures,

optionally a repellent and at least one binder.

According to a preferred embodiment of the invention, the mixtures according

to the present invention are employed via direct or soil application. Soil

application (incl. perimeter application) is especially favorable for use against

ants, termites, crickets, or cockroaches as well as soilborne fungi.

According to another preferred embodiment of the invention, for use against non

crop pests such as ants, termites, wasps, flies, mosquitoes, crickets, locusts, or

cockroaches the mixtures according to the present invention are prepared into a

bait preparation. The bait can be a liquid, a solid or a semisolid preparation (e.g.

a gel). The bait employed in the composition is a product which is sufficiently

attractive to incite insects such as ants, termites, wasps, flies, mosquitoes,

crickets etc. or cockroaches to eat it. This attractant may be chosen from feeding

stimulants or para and/or sex pheromones readily known in the art.

The mixtures according to the invention can be applied to any and all

developmental stages, e.g. for insect control: egg, larva, pupa, and adult. The

pests may be controlled by exposing the target pest, its food supply, habitat,

breeding ground or its locus with a pesticidally effective amount of the inventive

mixtures or of compositions comprising the mixtures.

"Locus" means a plant, seed, soil, area, material or environment in which a pest

is growing or may grow.

For non-crop use the compound (I) and the one or more compound(s) (II) are

usually applied in a weight ratio of from 1000:1 to 1:1000 as well as those

preferred ratios provided above for crop use. Depending on the desired effect,

the specific mixture partner(s), pest to be controlled, material to be protected

and/or weather condition the application rates of the mixtures according to the

invention are usually from 1 - 150 g/L.

Compositions of this invention may further contain other active ingredients than

those listed above. For example herbicides, fertilizers such as ammonium

nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth

regulators and safeners. These additional ingredients may be used sequentially

or in combination with the above-described compositions, if appropriate also

added only immediately prior to use (tank mix). For example, the plant(s) may

be sprayed with a composition of this invention either before or after being

treated with other active ingredients.

In general, pesticidally "effective amount" means the amount of the inventive

mixtures or of compositions comprising the mixtures needed to achieve an

observable effect on growth, including the effects of necrosis, death, retardation,

prevention, and removal, destruction, or otherwise diminishing the occurrence

and activity of the target organism. The effective amount can vary for the

various mixtures/compositions used in the invention. An effective amount of the

mixtures/compositions will also vary according to the prevailing conditions such

as desired pesticidal effect and duration, weather, target species, locus, mode of

application, and the like.

In the case of soil treatment or of application to the pests dwelling place or nest,

the quantity of active ingredient(s), by example, ranges from 0.0001 to 500 g per

100 m2, preferably from 0.001 to 20 g per 100 m2.

Customary application rates in the protection of materials are, for example, from

0.01 g to 1000 g of active compound(s) per m treated material, desirably from

0 .1 g to 50 g per m2.

Insecticidal compositions for use in the impregnation of materials typically

contain from 0.001 to 95 weight , preferably from 0.1 to 45 weight , and

more preferably from 1 to 25 weight % of at least one repellent and/or

insecticide.

For use in bait compositions, the typical content of active ingredient(s) is from

0.0001 weight % to 15 weight , desirably from 0.001 weight % to 5% weight

% of active compound. The composition used may also comprise other additives

such as a solvent of the active material, a flavoring agent, a preserving agent, a

dye or a bitter agent. Its attractiveness may also be enhanced by a special color,

shape or texture.

For use in spray compositions, the content of the mixture of the active

ingredients is from 0.001 to 80 weights , preferably from 0.01 to 50 weight %

and most preferably from 0.01 to 15 weight %.

In the context of the present invention, the term plant refers to an entire plant, a

part of the plant or the propagation material of the plant.

The mixtures of the present invention and the compositions comprising them are

particularly important in the control of a multitude of insects and/or pests (e.g.

fungi) on various cultivated plants, such as cereal, root crops, oil crops,

vegetables- and fruit spices, ornamentals, for example seed of durum and other

wheat, barley, oats, rye, maize (fodder maize and sugar maize / sweet and field

corn), soybeans, oil crops, crucifers, cotton, coffee, sunflowers, bananas, rice,

oilseed rape, turnip rape, sugarbeet, fodder beet, eggplants, potatoes, grass,

lawn, turf, fodder grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg

lettuce, pepper, cucumbers, melons, Brassica species, melons, beans, peas,

garlic, onions, carrots, tuberous plants such as potatoes, sugar cane, tobacco,

grapes, grapewines, petunias, geranium/pelargoniums, pansies and impatiens.

Plants which can be treated with the inventive mixtures include all genetically

modified plants or transgenic plants, e.g. crops which tolerate the action of

herbicides or fungicides or insecticides owing to breeding, including genetic

engineering methods, or plants which have modified characteristics in

comparison with existing plants, which can be generated for example by

traditional breeding methods and/or the generation of mutants, or by

recombinant procedures.

The term "cultivated plants" is to be understood as including plants which have

been modified by breeding, mutagenesis or genetic engineering. Genetically

modified plants are plants, which genetic material has been so modified by the

use of recombinant DNA techniques that under natural circumstances cannot

readily be obtained by cross breeding, mutations or natural recombination.

Typically, one or more genes have been integrated into the genetic material of a

genetically modified plant in order to improve certain properties of the plant.

Such genetic modifications also include but are not limited to targeted post-

transtional modification of protein(s) (oligo- or polypeptides) for example by

glycosylation or polymer additions such as prenylated, acetylated or

farnesylated moieties or PEG moieties (e.g. as disclosed in Biotechnol. Prog.

2001 Jul-Aug. 17(4), 720-8; Protein Eng. Des. Sel. 2004 Jan. 17(1), 57-66; Nat.

Protoc. 2007, 2(5), 1225-35; Curr. Opin. Chem. Biol. 2006 Oct 10(5), 487-91;

Epub. 2006, Aug 28.; Biomaterials. 2001 Mar. 22(5), 405-17; Bioconjug. Chem.

2005 Jan-Feb. 16(1): 1 13-21).

The term "cultivated plants" is to be understood also including plants that have

been rendered tolerant to applications of specific classes of herbicides, such as

hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase

(ALS) inhibitors, such as sulfonyl ureas (see e.g. US 6,222,100, WO 01/82685,

WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529,

WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or

imidazolinones (see e.g. US 6,222,100, WO 01/82685, WO 00/26390, WO

97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO

03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-

3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e.g. WO

92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g.

EP-A-0242236, EP-A-242246) or oxynil herbicides (see e.g. US 5,559,024) or

PPO herbicides, ACCase herbicides, 2,4-D and dicamba as a result of

conventional methods of breeding or genetic engineering. Several cultivated

plants have been rendered tolerant to herbicides by conventional methods of

breeding (mutagenesis), for example Clearfield summer rape (Canola) being

tolerant to imidazolinones, e.g. imazamox. Genetic engineering methods have

been used to render cultivated plants, such as soybean, cotton, corn, beets and

rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which

are commercialy available under the trade names RoundupReady (glyphosate)

and Liberty Link (glufosinate).

The term "cultivated plants" is to be understood also including plants that are by

the use of recombinant DNA techniques capable to synthesize one or more

insecticidal proteins, especially those known from the bacterial genus Bacillus,

particularly from Bacillus thuringiensis, such as a-endotoxins, e . g . CrylA(b),

CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bi) or Cry[theta]c;

vegetative insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A;

insecticidal proteins of bacteria colonizing nematodes, for example

Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as

scorpion toxins, arachnid toxins, wasp toxins, or other insect- specific

neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins,

such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin

inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors;

ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin,

saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxy steroid

oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone

inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of

sodium or calcium channels; juvenile hormone esterase; diuretic hormone

receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases

or glucanases. In the context of the present invention these insecticidal proteins

or toxins are to be understood expressly also as pre-toxins, hybrid proteins, trun

cated or otherwise modified proteins. Hybrid proteins are characterized by a

new combination of protein domains, (see, for example WO 02/015701). Further

examples of such toxins or genetically-modified plants capable of synthesizing

such toxins are disclosed, for example, in EP-A 374 753, WO 93/007278, WO

95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 and WO 03/052073.

The methods for producing such genetically modified plants are generally

known to the person skilled in the art and are described, for example, in the

publications mentioned above. These insecticidal proteins contained in the

genetically modified plants impart to the plants producing these proteins

protection from harmful pests from certain taxonomic groups of arthropods,

particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths

(Lepidoptera) and to plant parasitic nematodes (Nematoda).



proteins to increase the resistance or tolerance of those plants to bacterial, viral

or fungal pathogens. Examples of such proteins are the so-called " pathogenesis-

related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease

resistance genes (for example potato cultivars, which express resistance genes

acting against Phytophthora infestans derived from the mexican wild potato

Solanum bulbocastanum) or T4-lysozym (e.g. potato cultivars capable of

synthesizing these proteins with increased resistance against bacteria such as

Erwinia amylvora). The methods for producing such genetically modified plants

are generally known to the person skilled in the art and are described, for

example, in the publications mentioned above.



proteins to increase the productivity (e.g. bio mass production, grain yield,

starch content, oil content or protein content), tolerance to drought, nitrogen

utilization, salinity or other growth-limiting environmental factors or tolerance

to pests and fungal, bacterial or viral pathogens of those plants.

The term "cultivated plants" is to be understood also including plants that

contain by the use of recombinant DNA techniques a modified amount of

substances of content or new substances of content, specifically to improve

human or animal nutrition, for example oil crops that produce health-promoting

long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e.g. Nexera

rape). The term "cultivated plants" is to be understood also including plants that

contain by the use of recombinant DNA techniques a modified amount of

substances of content or new substances of content, specifically to improve raw

material production, for example potatoes that produce increased amounts of

amylopectin (e.g. Amflora potato).

Some of the inventive mixtures have systemic action and can therefore be used

for the protection of the plant shoot against foliar pests as well as for the

treatment of the seed and roots against soil pests.

The mixtures according to the present invention are also suitable for the

protection of plant propagation material including treatment of seeds in order to

protect the seed from insect pest, in particular from soil-living insect pests;

and/or fungi and the resulting plant's roots and shoots against soil pests and

foliar insects and/or fungi. The protection of the resulting plant's roots and

shoots is preferred.

More preferred is the protection of resulting plant's shoots from piercing and

sucking insects.

The present invention therefore comprises a method for the protection of seeds

from insects and fungi, in particular from soil insects and of the seedlings' roots

and shoots from insects, in particular from soil and foliar insects, said method

comprising contacting the seeds before sowing and/or after pre-germination with

mixtures according to the present invention. Particularly preferred is a method,

wherein the plant's roots and shoots are protected, more preferably a method,

wherein the plants shoots are protected from piercing and sucking insects, most

preferably a method, wherein the plants shoots are protected from such pests as

aphids, spider mite, army worm, leaf hopper, European corn borer, cutworm,

corn ear worm, corn root worm, stink bugs, plant bug, wireworm, codling moth,

and navel orange worm.

The term seed embraces seeds and plant propagules of all kinds including but

not limited to true seeds, seed pieces, suckers, corms, bulbs, fruit, tubers, grains,

cuttings, cut shoots and the like and means in a preferred embodiment true

seeds. The application methods according to the invention for the protection of

plant propagation material are characterized in that, for example, the

composition are applied in such a manner that it is applied in close spatial

proximity to, or spatially together with, planting or sowing the plant propagation

material at the site of planting or sowing. Application of the composition in

close spatial proximity to the site of planting or sowing takes place preferably

when planting or sowing the plant propagation material, by applying the

compositions by soil application directly to the site where the plant propagation

material has been planted or sown, for example preferably when sowing into the

seed furrow, or to a closely delimited area around the site of planting or sowing

the plant propagation material. In addition, the mixture composition (compound

(I) + (II)) will create a zone of protection in the soil, which controls the pests in

the soil, but also the roots and stems, when contacted with the soil containing

the composition, absorb the composition, and then distribute the composition

throughout the plant through known means. Application of such compositions,

which takes place spatially together with planting or applying the plant

propagation material to the site of planting or sowing is to be understood as

meaning that plant propagation material which has been pretreated with these

compositions is planted or sown at the site of planting or sowing, it being

possible, depending on the intended aims and prevailing circumstances, for the

pretreatment of the plant propagation material to be affected for example by

spraying, atomizing, dusting or scattering the compositions over the plant

propagation material or brushing or pouring the compositions over the plant

propagation material or, in the event of seed, in particular also by dressing the

seed. When carrying out seed dressing, i.e. dry seed, wet seed-dressing, liquid

seed-dressing or slurry dressing, mixture composition is added to the seed prior

to sowing in a seed-dressing apparatus and the composition is distributed

uniformly over the seed, for example by stirring the contents of the seed-

dressing apparatus and/or by rotating and/or shaking the entire seed-dressing

apparatus. Particular embodiments of such a seed-dressing treatment comprise,

for example, immersing the seed in a liquid composition, coating the seed with a

solid composition (seed coating) or by achieving penetration of the active

ingredient into the seed by adding the composition to the water used for pre-

soaking the seed (seed soaking). For a general discussion of techniques used to

apply pesticides to seeds, see "Seed Treatment," 2d ed., (1986), edited by K.A

Jeffs (chapter 9), herein incorporated by reference in its entirety.

The term "seed treatment" comprises all suitable seed treatment techniques

known in the art, such as seed dressing, seed coating, seed dusting, seed soaking

and seed pelleting.

Preferred application methods are:

(A) Seed treatment, wherein the seed is treated with the mixture

composition prior to planting the seed;

(B) Preemergence or postemergence application.

i . Preemergence refers to application of the mixture composition

before the plants has emerged from the soil.

ii. Postemergence refers to application of the mixture composition

after the plant has emerged from the soil. For example the

mixture composition is sprayed directly at the stem base, leaves,

or soil interface of the plants;

(C) In-furrow application.

i . T-band application wherein the mixture composition is added

before the furrow is closed, but after the plant propagation

material is added to the opened furrow; or after the furrow has

been closed.

ii. Modified in-furrow application wherein a plant propagation

material is placed in an open furrow and the mixture composition

is added such that it surrounds the plant propagation material, but

minimizes the contact with the plant propagation material;

iii. granular application, either on fertilizer or a solid carrier applied

in-furrow or potentially on side of furrow;

(D) Band spray application, wherein the mixture composition is sprayed

onto the soil before

i . planting the plant propagation material; or

ii. planting the plant propagation material, and also incorporated the

mixture composition into the soil;

(E) Irrigation either by

i . drip

ii. trickle on demand systems; or

iii. higher volume chemigation systems;

(F) At transplanting by

i . dipping, wherein transplants is dipped into the mixture

composition prior to transplanting

ii. Drenching, wherein transplants are drenched with a mixture

composition after transplanting;

The present invention also comprises seeds coated with or containing the active

compound(s). The term "coated with and/or containing" generally signifies that

the active ingredient(s) are for the most part on the surface of the propagation

product at the time of application, although a greater or lesser part of the

ingredient may penetrate into the propagation product, depending on the method

of application. When the said propagation product is (re)planted, it may absorb

the active ingredient(s). Suitable seeds are seeds of cereals, root crops, oil crops,

vegetables, spices, ornamentals, for example seed of durum and other wheat,

barley, oats, rye, maize (fodder maize and sugar maize / sweet and field corn),

soybeans, oil crops, crucifers, cotton, sunflowers, bananas, rice, oilseed rape,

turnip rape, sugar beet, fodder beet, eggplants, potatoes, grass, lawn, turf, fodder

grass, tomatoes, leeks, pumpkin/squash, cabbage, iceberg lettuce, pepper,

cucumbers, melons, Brassica species, melons, beans, peas, garlic, onions,

carrots, tuberous plants such as potatoes, sugar cane, tobacco, grapes, petunias,

geranium/pelargoniums, pansies and impatiens.

In addition, the mixtures according to the invention may also be used for the

treatment of seeds from plants, which tolerate the action of herbicides or

fungicides or insecticides owing to breeding, including genetic engineering

methods.

For example, the active mixtures can be employed in treatment of seeds from

plants, which are resistant to herbicides from the group consisting of the

sulfonylureas, imidazolinones, glufosinate-ammonium or glyphosate-

isopropylammonium and analogous active substances (see for example, EP-A-

0242236, EP-A-0242246) (WO 92/00377) (EP-A-0257993, U.S. Pat. No.

5,013,659) or in transgenic crop plants, for example cotton, with the capability

of producing Bacillus thuringiensis toxins (Bt toxins) which make the plants

resistant to certain pests (EP-A-0142924, EP-A-0193259).

Furthermore, the mixtures according to the present invention can be used also

for the treatment of seeds from plants, which have modified characteristics in

comparison with existing plants consist, which can be generated for example by

traditional breeding methods and/or the generation of mutants, or by

recombinant procedures). For example, a number of cases have been described

of recombinant modifications of crop plants for the purpose of modifying the

starch synthesized in the plants (e.g. WO 92/11376, WO 92/14827, WO

91/19806) or of transgenic crop plants having a modified fatty acid composition

(WO 91/13972).

The seed treatment application of the mixtures is carried out by spraying or by

dusting the seeds before sowing of the plants and before emergence of the

plants.

In the treatment of seeds the corresponding formulations are applied by treating

the seeds with an effective amount of the mixture according to the present

invention. Herein, but depending on the desired effect, the specific mixture

partner(s), pest to be controlled, seed material to be protected and/or weather

condition, the application rates of the active compound(s) are generally from

0.01 g to 10 kg per 100 kg of seed, preferably from 0.1 g to 5 kg per 100 kg of

seed, in particular from 1 g to 2.5 kg per 100 kg of seed.

Compositions, which are especially useful for seed treatment are e.g.:

A) Soluble concentrates (SL, LS), D) Emulsions (EW, EO, ES), E) Suspensions

(SC, OD, FS), F) Water-dispersible granules and water-soluble granules (WG,

SG) G) Water-dispersible powders and water-soluble powders (WP, SP, WS),

H) Gel-Formulations (GF), I) Dustable powders (DP, DS).

Conventional seed treatment formulations include for example flowable

concentrates FS, suspension concentrates SC, solutions LS, powders for dry

treatment DS, water dispersible powders for slurry treatment WS, water-soluble

powders SS and emulsion ES and EC and gel formulation GF. These

formulations can be applied to the seed diluted or undiluted. Application to the

seeds is carried out before sowing, either directly on the seeds or after having

pre- germinated the latter.

In a preferred embodiment a SC or FS formulation is used for seed treatment.

Typcially, a SC or FS concentrated formulation, e.g. for seed treatment use, may

comprise 1-800 g/1 of active ingredients, 1-200 g/1 Surfactant, 0-200 g/1

antifreezing agent, 0- 400 g/1 of binder, 0-200 g/1 of a pigment and up to 1 liter

of a solvent, preferably water.

Preferred FS formulations of mixtures disclosed herein for seed treatment

usually comprise from 0.1 to 80% by weight ( 1 to 800 g/1) of the active

ingredient(s), from 0.1 to 20 % by weight ( 1 to 200 g/1) of at least one

surfactant, e.g. 0.05 to 5 % by weight of a wetter and from 0.5 to 15 % by

weight of a dispersing agent, up to 20 % by weight, e.g. from 5 to 20 % of an

anti-freeze agent, from 0 to 15 % by weight, e.g. 1 to 15 % by weight of a

pigment and/or a dye, from 0 to 40 % by weight, e.g. 1 to 40 % by weight of a

binder (sticker /adhesion agent), optionally up to 5 % by weight, e.g. from 0.1 to

5 % by weight of a thickener, optionally from 0 .1 to 2 % of an anti-foam agent,

and optionally a preservative such as a biocide, antioxidant or the like, e.g. in an

amount from 0.01 to 1 % by weight and a filler/vehicle up to 100 % by weight.

Seed treatment formulations may additionally also comprise binders and

optionally colorants.

Binders can be added to improve the adhesion of the active materials on the

seeds after treatment. Suitable binders are block copolymers EO/PO surfactants

but also polyvinylalcohols, polyvinylpyrrolidones, polyacrylates,

polymethacrylates, polybutenes, polyisobutylenes, polystyrene,

polyethyleneamines, polyethyleneamides, polyethyle-neimines, polyethers,

polyurethans, polyvinylacetate, tylose and copolymers derived from these

polymers.

Optionally, also colorants can be included in the formulation. Suitable colorants

or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112,

C.I. Solvent Red 1, pigment blue 15:4, pigment blue 15:3, pigment blue 15:2,

pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13,

pigment red 112, pigment red 48:2, pigment red 48:1, pigment red 57: 1, pigment

red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment

green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10,

basic violet 49, acid red 51, acid red 52, acid red 14, acid blue 9, acid yellow 23,

basic red 10, basic red 108.

Animal health application

The present invention also includes a method of controlling animal pests which

comprises the exposure of the animal pests, their habit, breeding ground, food

supply, cultivated plants, seed, soil, area, material or environment in which the

animal pests are growing or may grow, or the materials, plants, seeds, soils,

surfaces or spaces to be protected from animal attack or infestation with a

pesticidally effective amount of a mixture of at least one active compound (I)

and at least one active compound (II). Preferred application methods are into

water bodies, via soil, cracks and crevices, pastures, manure piles, sewers, into

water, on floor, wall, or by perimeter spray application and bait.

For use of the combination for controlling pests in and on animals, the present

invention also provides a method for treating, controlling, preventing and

protecting animals against infestation and infection by the harmful pests (e.g.

parasites), which comprises orally, topically or parenterally administering or

applying to the animals a pesticidal (e.g parasiticidally) effective amount of

mixture of the present invention or a composition comprising it. Preferably for

animal use the compound (I) is mixed with one or more compounds (II) with

insectricidal, acaricidal or nematicidal activity.

Amounts and ratios of the compound (I) and (II) depends on the desired effect,

the specific mixture partner(s), pest to be controlled and animal to be treated.

The compound (I) and the one or more compound(s) (II) are usually applied in a

weight ratio of from 1000:1 and 1:1000. In other embodiments that weight ratio

of (I) to (II) may be between 500:1 to 1:500, for example between 100:1 to

1:100, for example between 1:50 to 50:1, for example 1:20 to 20:1, for example

1:10 to 10:1, for example 1:5 to 5:1. Other examples of weight ratios of (I) to

(II) include 1:1, 1:2, 1:3, 1:4, 2:1, 3:1, 4:1.

Administration can be carried out both prophylactically and therapeutically.

Administration of the active compounds is carried out directly or in the form of

suitable preparations, orally, topically/dermally or parenterally.

For oral administration to warm-blooded animals, the mixtures of the present

invention may be formulated as animal feeds, animal feed premixes, animal feed

concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses

and capsules. In addition, the mixtures of the present invention may be

administered to the animals in their drinking water. For oral administration, the

dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of

animal body weight per day of the compounds (I)+(II), preferably with 0.5

mg/kg to 100 mg/kg of animal body weight per day.

Alternatively, the mixtures of the present invention may be administered to

animals parenterally, for example, by intraruminal, intramuscular, intravenous

or subcutaneous injection. The compound (I) and (II) may be dispersed or

dissolved in a physiologically acceptable carrier for subcutaneous injection.

Alternatively, the mixtures of the present invention may be formulated into an

implant for subcutaneous administration. In addition the compounds (I) + (II)

may be transdermally administered to animals. For parenteral administration, the

dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of

animal body weight per day of the active compounds.

The mixtures of the present invention may also be applied topically to the

animals in the form of dips, dusts, powders, collars, medallions, sprays,

shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or

water-in-oil emulsions. For topical application, dips and sprays usually contain

0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the active

compounds. In addition, the active compound mixtures may be formulated as

ear tags for animals, particularly quadrupeds such as cattle and sheep.

Suitable preparations are:

- Solutions such as oral solutions, concentrates for oral administration after

dilution, solutions for use on the skin or in body cavities, pouring-on

formulations, gels;

- Emulsions and suspensions for oral or dermal administration; semi-solid

preparations;

- Formulations in which the active compound is processed in an ointment base

or in an oil-in-water or water-in-oil emulsion base; - Solid preparations such as

powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules;

aerosols and inhalants, and active compound-containing shaped articles.

Compositions suitable for injection are prepared by dissolving the active

ingredient in a suitable solvent and optionally adding further ingredients such as

acids, bases, buffer salts, preservatives, and solubilizers. The solutions are

filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water, alkanols

such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol,

polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, and mixtures

thereof.

The active compounds can optionally be dissolved in physiologically tolerable

vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of the active

compound in the main solvent or prevent its precipitation. Examples are

polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and

polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic

acid esters, and n-butanol. Oral solutions are administered directly. Concentrates

are administered orally after prior dilution to the use concentration. Oral

solutions and concentrates are prepared according to the state of the art and as

described above for injection solutions, sterile procedures not being necessary.

Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on

or sprayed on.

Solutions for use on the skin are prepared according to the state of the art and

according to what is described above for injection solutions, sterile procedures

not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy

ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as

alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such

as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic

oils, dimethylformamide, dimethylacetamide, transcutol, solketal,

propylencarbonate, and mixtures thereof.

It may be advantageous to add thickeners during preparation. Suitable thickeners

are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium

monostearate, organic thickeners such as cellulose derivatives, polyvinyl

alcohols and their copolymers, acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into body cavities. Gels

are prepared by treating solutions which have been prepared as described in the

case of the injection solutions with sufficient thickener that a clear material

having an ointment-like consistency results. The thickeners employed are the

thickeners given above.

Pour-on formulations are poured or sprayed onto limited areas of the skin, the

active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending or emulsifying the

active compound in suitable skin-compatible solvents or solvent mixtures. If

appropriate, other auxiliaries such as colorants, bioabsorption-promoting

substances, antioxidants, light stabilizers, adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethylene glycols,

polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol,

phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate,

benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene

glycol monomethyl ether, di-ethylene glycol mono-butyl ether, ketones such as

acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate,

ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or

synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as

methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone,

N-methylpyrrolidone, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene- 1,3-

dioxolane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals and which can

be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO, spreading

oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils

and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty

alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassium

metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole,

tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starch derivatives,

polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-water type.

They are prepared by dissolving the active compound either in the hydrophobic

or in the hydrophilic phase and homogenizing this with the solvent of the other

phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries

such as colorants, absorption-promoting substances, preservatives, antioxidants,

light stabilizers, viscosity-enhancing substances.

Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils, natural

vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides

such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty

acids of the chain length C5-C22 or other specially selected natural fatty acids,

partial glyceride mixtures of saturated or unsaturated fatty acids possibly also

containing hydroxyl groups, mono- and diglycerides of the C5-C12 fatty acids,

fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate,

dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain

length with saturated fatty alcohols of chain length C16-C18, isopropyl

myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty

alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate,

ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck

coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures

related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol,

cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and

mixtures thereof.

Suitable hydrophilic phases are: water, alcohols such as propylene glycol,

glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil,

polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol

monostearate, poly-oxyethyl stearate, alkylphenol polyglycol ether; ampholytic

surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic

surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates,

mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine

salt; cation-active surfactants, such as cetyltrimethylammonium chloride.

Suitable further auxiliaries are: substances which enhance the viscosity and

stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and

other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum

arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl

ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or

mixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They are prepared

by suspending the active compounds in a suspending agent, if appropriate with

addition of other auxiliaries such as wetting agents, colorants, bioabsorption-

promoting substances, preservatives, antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solvent mixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally or topically/dermally. They

differ from the suspensions and emulsions described above only by their higher

viscosity.

For the production of solid preparations, the active compound is mixed with

suitable excipients, if appropriate with addition of auxiliaries, and brought into

the desired form. Suitable excipients are all physiologically tolerable solid inert

substances. Those used are inorganic and organic substances. Inorganic

substances are, for example, sodium chloride, carbonates such as calcium

carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids,

argillaceous earths, precipitated or colloidal silica, or phosphates. Organic

substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk

powder, animal meal, grain meals and shreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have

been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesium

stearate, stearic acid, talc, bentonites, disintegration-promoting substances such

as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or

linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.

The compositions for use in or on animals can comprise generally from about

0.001 to 95 wt of the active compounds of the mixtures of the present

invention.

Generally it is favorable to apply the active compounds of the mixtures of the

present invention in total amounts of 0.5 mg/kg to 100 mg/kg per day,

preferably 1 mg/kg to 50 mg/kg per day.

Ready-to-use preparations contain the active compounds of the mixtures of the

present invention acting against pests such as parasites, preferably ecto

parasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from

0 .1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight,

most preferably from 5 to 40 per cent by weight.

Preparations which are diluted before use contain the active compounds of the

mixtures of the present invention acting against ectoparasites in concentrations

of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.

Furthermore, the preparations comprise the active compounds of the mixtures of

the present invention against endoparasites in concentrations of 10 ppm to 2 per

cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly

preferably of 0.005 to 0.25 per cent by weight.

In a preferred embodiment of the present invention, the compositions

comprising the mixtures of the present invention are applied dermally/topically.

In a further preferred embodiment, the topical application is conducted in the

form of compound-containing shaped articles such as collars, medallions, ear

tags, bands for fixing at body parts, and adhesive strips and foils.

Generally it is favorable to apply solid formulations which release the active

compounds of the mixtures of the present invention in total amounts of 10

mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25

mg/kg to 160 mg/kg body weight of the treated animal in the course of three

weeks.

For the preparation of the shaped articles, thermoplastic and flexible plastics as

well as elastomers and thermoplastic elastomers are used. Suitable plastics and

elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins,

cellulose, cellulose derivatives, polyamides and polyester which are sufficiently

compatible with the compound (I). A detailed list of plastics and elastomers as

well as preparation procedures for the shaped articles is given e.g. in WO

03/086075.

Biological efficacy

The weight ratio of compound (I) to compound(s) (II) is selected to provide a

synergistic pesticidal action, i.e. the compound(s) (I) be is present in an activity

enhancing amount with respect to compound(s) (II) or vica versa.

A synergistic effect exists whenever the action of a combination of two

chemicals is greater than the sum of the action of each of the chemicals alone.

Therefore, a synergistic combination is a combination of chemical components

having an action that is greater than the sum of the action of each chemical

component alone, and a synergistically effective amount is an effective amount

of a synergistic combination. Synergism can involve either 2 pesticides, or one

pesticide plus a substance that is not by itself toxic to the pest, and such a

substance is termed a synergist, i.e. a chemical that enhances the toxicity of a

pesticide to a pest.

Well-known methods for determining whether synergy exists include the Colby

method, the Tammes method and the Wadley method, all of which are described

below. Any one of these methods may be used to determine if synergy exists

between the compounds (I) and (II).

In the Colby method, also referred to as the Limpels method, the action to be

expected E for a given active ingredient combination obeys the so-called Colby

formula. According to Colby, the expected action of ingredients (I)+(II) using

p+q ppm of active ingredient is:

where ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture

X=% action by compound (I) using p ppm of active ingredient Y=% action by

compound (II) using q ppm of active ingredient. If the ratio R defined as the

action actually observed (O) divided by the expected action (E) is > 1 then the

action of the combination is superadditive, i.e. there is a synergistic effect. For a

more detailed description of the Colby formula, see Colby, S. R. "Calculating

synergistic and antagonistic responses of herbicide combination," Weeds, Vol.

15, pages 20-22; 1967; see also Limpel et al., Proc. NEWCC 16: 48-53 (1962).

The Tammes method uses a graphic representation to determine whether a

synergistic effect exists. See "Isoboles, a graphic representation of synergism in

pesticides," Netherlands Journal of Plant Pathology, 70 (1964) p . 73-80.

The Wadley method is based on comparison of an observed ED50 value (i.e.

dose of a given compound or combination of compounds providing 50% pest

control) obtained from experimental data using the dose response curves and an

expected ED50 calculated theoretically from the formula:

ED ((I) + (II))p

= a +

ED (I)obs

ED (II)obs

wherein a and b are the weight ratios of compound (I) and (II) in the mixture

and EDsoobs the experimentally determined ED50 value obtained using the dose

response curves for the individual compounds. The ratio

ED5o((I)+(II ))expected/ED5o((I)+(II))observed expresses the factor of interaction (F)

(synergy factor). In case of synergism, F is >1. The same formula applies when

LD50 values are used, i.e. lethal dose, as well as EC50 values, i.e. effective

concentration, and LC50 values, i.e. lethal concentration. For a more detailed

description of the Wadley method, see Levi et al., EPPO-Bulletin 16, 1986, 651-

657.

An alternative approach as mentioned by D.L. Richer (Pesticide Science, 1987,

19, 309-315, especially p . 313) to determine synergy is based on purely

observed values rather than observed and theoretical calculated values as used in

the previously mentioned methods. In this alternative method the effect of a

given rate of the mixture A and B is compared with the effect of the same rate of

each of (I) and (II) used alone. If synergism exists, the observed effect of the

mixture will be greater than the observed effect of either component used alone:

Eo s

(x(I) + y(II))> Eo s

(x + y)(I), and > Eo s

(x + y)(II)

wherein x and y are the quantities of (I) and (II) in the mixture.

Examples

Comparative example 1

The compound (I) was tested in comparison with its (IS, cis)-enantiomer, i.e.

the compound 2-methylbiphenyl-3-ylmethyl (Z)-(lS)-cis-3-(2-chloro-3,3,3-

trifluoroprop-l-enyl)-2,2-dimethylcyclopropane-carboxylate (compound (1,5).

Two seperate trials were conducted using doses of lOng/insect and 30ng/insect

of each compound applied in each trial to 10 individual insects respectively,

Dysdercus cingulatus (cotton stainer), by topical application in a non-

randomized petridish trial using 5 replicas for each compound. The actives were

applied as acetone formulations (blank acetone did not demonstrate any effect).

Similar a series of test were conducted on Musca domestica (housefly). Average

results based on visual evaluation are found in table 3 below for

a) immobilized (paralyzed/dead) insects after 4 hours; and

b) dead insects (mortality asessment= NUMINS number of dead insects)

observed after 48 hours.

Table 3 : Comparative test for compound (I) and compound (1,5).

1. Activity against Southern armyworm (Spodoptera eridania), 2nd instar

larvae

The active compounds are formulated for testing the activity against insects and

arachnids as a 10.000 ppm solution in a mixture of 35% acetone and water,

which is diluted with water, if needed.

A Sieva lima bean leaf is dipped in the test solution and allowed to dry. The leaf

is then placed in a petri dish containing a filter paper on the bottom and ten 2nd

instar caterpillars. At 5 days, observations are made of mortality and reduced

feeding.

2. Activity against diamond back moth (plutella xylostella)

The active compounds are formulated in 50:50 acetone:water and 0.1 %

(vol/vol) Alkamuls EL 620 surfactant. A 6 cm leaf disk of cabbage leaves is

dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate

lined with moist filter paper. The leaf disk is inoculated with 10 third instar

larvae and kept at 25-27 and 50-60% humidity for 3 days. Mortality is assessed

after 72 h of treatment.

3. Activity against cowpea aphid {aphis craccivora)

The active compounds were formulated in 50:50 acetone:water. Potted cowpea

plants colonized with 100 - 150 aphids of various stages were sprayed after the

pest population has been recorded. Population reduction was recorded after 24,

72, and 120 hours.

4. Activity against Vetch aphid (Megoura viciae)

The active compounds are formulated in 1:3 DMSO : water. Bean leaf disks are

placed into microtiterplates filled with 0.8% agar-agar. The leaf disks are

sprayed with 2.5 µΐ of the test solution and 5 to 8 adult aphids are placed into the

microtiterplates which are then closed and kept at a temperature of 22-24°C and

35-45% relative humidity under fluorescent light for 6 days. Mortality is

assessed on the basis of vital, reproduced aphids. Tests are replicated 2 times.

5. Activity against Wheat aphid (Rhopalosiphum padi)

The active compounds are formulated in 1:3 DMSO : water. Barley leaf disks

are placed into microtiterplates filled with 0.8% agar-agar. The leaf disks are

sprayed with 2.5 µΐ of the test solution and 3 to 8 adult aphids are placed into the

microtiterplates which are then closed and kept at a temperature of 22-24°C and

35-45% relative humidity under fluorescent light for 5 days. Mortality is

assessed on the basis of vital aphids. Tests are replicated 2 times.

6. Activity against Cotton aphid {Aphis gossypii)

The active compounds were formulated in 50:50 acetone:water and 100 ppm

Kinetic surfactant.

Cotton plants at the cotyledon stage (one plant per pot) were infested by placing

a heavily infested leaf from the main colony on top of each cotyledon. The

aphids were allowed to transfer to the host plant overnight, and the leaf used to

transfer the aphids was removed. The cotyledons were dipped in the test solution

and allowed to dry. After 5 days, mortality counts were made.

7. Activity against silverleaf whitefly (bemisia argentifolu)


Kinetic surfactant.

Selected cotton plants were grown to the cotyledon state (one plant per pot). The

cotyledons were dipped into the test solution to provide complete coverage of

the foliage and placed in a well-vented area to dry. Each pot with treated

seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately

3-5 day old) were introduced. The insects were collected using an aspirator and

an 0.6 cm, non-toxic Tygon tubing (R-3603) connected to a barrier pipette tip.

The tip, containing the collected insects, was then gently inserted into the soil

containing the treated plant, allowing insects to crawl out of the tip to reach the

foliage for feeding. The cups were covered with a re-usable screened lid (150

micron mesh polyester screen PeCap from Tetko Inc). Test plants were

maintained in the holding room at about 25°C and 20-40% relative humidity for

3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to

prevent trapping of heat inside the cup. Mortality was assessed 3 days after

treatment of the plants.

8. Green Peach Aphid (Myzus persicae)


Kinetic surfactant.

Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') were

infested with approximately 40 laboratory-reared aphids by placing infested leaf

sections on top of the test plants. The leaf sections were removed after 24 hr.

The leaves of the intact plants were dipped into gradient solutions of the test

compound and allowed to dry. Test plants were maintained under fluorescent

light (24 hour photoperiod) at about 250°C and 20-40% relative humidity.

Aphid mortality on the treated plants, relative to mortality on check plants, was

determined after 5 days.

9. Activity against Musca (Musca domestica)

The active compounds were formulated in acetone.

The topical application comprised application of a single 2-µ1drop to the dorsal

thorax using an Arnold Hand-Operated Applicator (Burkard Manufacturing Co.,

Herts, England). Treated insects are transferred to observation chambers. The

dose-mortality relationship for each compound is assessed after 4, 24 and 48

hours (5 insects treated per dose) from four doses or with acetone alone

(control).

10. Synergistic effect between the compound (I) and abamectin (ABA).

Appropriate doses of the active ingredients were applied to the insects,

Dysdercus cingulatus (cotton stainer), both as single applications as well as

mixtures thereof by topical application in a non-randomized petridish trial.

Following visual evaluation of efficacy (mortality) at selected hours after

treatment (HAT), synergy was determined using Colby's formula.

Assessment= NUMINS (number of dead insects). The actives were applied as

acetone formulations. As control test a blank acetone formulation was also

applied to ensure non-effect from the solvent.

As comparative test, similar applications were made using a double dose of

bifenthrin (BIF) compared to the amount of the compound (I).

Results provided in table 4 .

Table 4 : Result of test for a combination of compound (I) and abamectin (ABA)

4HAT

Rate Observed Expected R

(ng/insect) effect effect

Compound (I) 5 6.8

BIF 10 8.6

ABA 5 0.2

ABA 10 0.2

Compound (I) 5+5 7.0 6.86 1.02

+ABA

BIF+ABA 10+10 6.6 8.63 0.76

24HAT



Compound (I) 5 6.8

BIF 10 7.0

ABA 5 0.2

ABA 10 0.2

Compound (I) 5+5 7.2 6.86 1.05

+ABA

BIF+ABA 10+10 5.4 7.00 0.77

48HAT



Compound (I) 5 7.0

BIF 10 7.0

ABA 5 0.2

ABA 10 0.4

Compound (I) 5+5 6.8 7.06 0.96

+ABA

BIF+ABA 10+10 5.4 7.12 0.76

11. Synergistic effect between the compound (I) and gamma-cyhalothrin

(GCH).

Same procedure as in example 10, with results as provided in table 5 :

Table 5 : Result of test for a combination of compound (I) and gamma-

cyhalothrin.

4HAT



Compound (I) 5 6.8

BIF 10 8.6

GCH 0.625 8.4

GCH 1.25 9.8

Compound (I) 5+0.625 10 9.49 1.05

+GCH

BIF +GCH 10+1,25 9.8 9.97 0.98

24HAT



Compound (I) 5 6.8

BIF 10 7.0

GCH 0.625 7.2

GCH 1.25 9.8

Compound (I) 5+0.625 9.8 9.10 1.08

+GCH

BIF +GCH 10+1.25 10 9.94 1.01

48HAT



Compound (I) 5 7.0

BIF 10 7.0

GCH 0.625 4.8

GCH 1.25 9.2

Compound (I) 5+0.625 10 8.4 1.18

+GCH

BIF +GCH 10+1.25 10 9.8 1.02

12. Synergistic effect between the compound (I) and dimethoate (DMT).


5 Table 6 : Result of test for a combination of compound (I) and dimethoate

(DMT)

4HAT



Compound (I) 5 4.6

BIF 10 5.6

DMT 50 0

DMT 100 0

Compound (I) 5+50 4.8 4.6 1.04

+ DMT

BIF + DMT 10+100 4.6 5.6 0.82

10 24HAT



Compound (I) 5 3.6

BIF 10 4.0

DMT 50 3.3

DMT 100 7.2

Compound (I) 5+50 7.0 5.0 1.4

+ DMT

BIF + DMT 10+100 9.2 8.3 0.82

72HAT

13. Synergistic effect between the compound (I) and acetamiprid (AMP).


Table 7 : Result of test for a combination of compound (I) and acetamiprid

(AMP)

48HAT



Compound (I) 5 8.0

BIF 10 8.0

AMP 25 5.2

Compound (I) 5+25 9.8 9.0 1.09

+AMP

BIF +AMP 10+25 9.2 9.0 1.02

72HAT

14. Synergistic effect between the compound (I) and methoxyfenozide

(MTZ).

Same procedure as in example 10, with results as provided in table 8:

Table 8: Result of test for a combination of compound (I) and methoxyfenozide

(MTZ)

4HAT

Rate R

(ng/insect)

Compound (I) 5+12 1.52

+ MTZ

BIF + MTZ 10+12 1.0

15. Synergistic effect between the compound (I) and chlorpyrifos (CPF).


Table 9 : Result of test for a combination of compound (I) and chlorpyrifos

(CPF)

4HAT

Rate R

(ng/insect)

Compound (I) 5+95 1.35

+ CPF

BIF + CPF 10+95 1.04

P A T E N T C L A I M S

1. A mixture of the compound (I) which is 2-methylbiphenyl-3-ylmethyl (Z)-

( 1 )-c -3-(2-chloro-3,3,3-trifluoroprop-l-enyl)-2,2-

dimethylcyclopropanecarboxylate and one or more of compound(s) (II)

which is an insecticide, acaricide, nematicide and/or fungicide.

2 . A mixture according to claim 1, wherein the compound (I) is substantially

free of any other isomer of 2-methylbiphenyl-3-ylmethyl 3-(2-chloro-3,3,3-

trifluoroprop- l-enyl)-2,2-dimethylcyclopro-panecarboxylate.

3 . A mixture according to claim 1 and 2 having insecticidal, nematicidal or

acaricidal activity.

4 . A mixture according to any of claims 1 to 3 wherein the compound(s) (II) is

an insecticide, acaricide and/or nematicide selected among

Acetylcholinesterase (AChE) inhibitors, GABA-gated chloride channel

antagonists, Sodium channel modulators/voltage-dependent sodium channel

blockers, Nicotinergic acetylcholine receptor agonists, Allosteric

acetylcholine receptor modulators, Chloride channel activators, Juvenile

hormone mimics, gassing agents, Selective homopteran feeding blockers,

Mite growth inhibitors, Microbial disruptors of insect midgut membranes,

Inhibitors of mitochondrial ATP synthase, Uncouplers of oxidative

phosphorylation. Nicotinic acetylcholine receptor channel blockers,

Inhibitors of chitin biosynthesis type 0 and 1, Moulting disruptors,

Ecdysone receptor agonists/disruptors, Octopamine receptor agonists,

Mitochondrial complex III electron transport inhibitors, Mitochondrial

complex I electron transport inhibitors, Voltage-dependent sodium channel

blockers, Inhibitors of acetyl CoA carboxylase, Mitochondrial complex IV

electron inhibitors, Mitochondrial complex II electron transport inhibitors,

and Ryanodine receptor modulators.

A mixture according to claim 4 wherein compound(s) (II) is selected among

Benzoylureas, Juvenile hormone mimics, Organophosphates,

Phenylpyrazoles, Pyrethroids, Chloronicotinyls, Avermectins,

Diacylhydrazines, Ryanodine receptor modulators and Spinosyns.

A mixture according to claim 5 wherein the compound(s) (II) is selected

among lufenuron, novaluron, pyriproxyfen, chlorpyrifos, chlorpyrifos-

methyl, dimethoate, malathion, fipronil, ethiprole, deltamethrin, lambda-

cyhalothrin, gamma-cyhalothrin, tefluthrin, acetamiprid, imidacloprid,

thiacloprid, thiamethoxam, abamectin, emmamectin-benzoate,

methoxyfenozide, flubendiamide, chlorantraniliprole cyantraniliprole,

spinosad and spinetoram.

A mixture accrding to any of claims 1 to 2 wherein the compound(s) (II) is

selected among fungicides.

A mixture according to claim 7 wherein the compound(s) (II) is selected

among methyl benzimidazole carbamate (MBC) fungicides; dicarboximide

fungicides; demethylation inhibitor (DMI) fungicides; phenylamide

fungicides; amine/morpholine fungicides; phospholipid biosynthesis

inhibitor fungicides; carboxamide fungicides; hydroxy(2-amino-)pyrimidine

fungicides; anilinopyrimidine fungicides; N-phenyl carbamate fungicides;

quinone outside inhibitor (Qol) fungicides; phenylpyrrole fungicides;

quinoline fungicides; lipid peroxidation inhibitor fungicides; melanin

biosynthesis inhibitors-reductase (MBI-R) fungicides; melanin biosynthesis

inhibitors-dehydratase (MBI-D) fungicides; hydroxyanilide fungicides;

squalene-epoxidase inhibitor fungicides; polyoxin fungicides; phenylurea

fungicides; quinone inside inhibitor (Qil) fungicides; benzamide fungicides;

enopyranuronic acid antibiotic fungicides; hexopyranosyl antibiotic

fungicides; glucopyranosyl antibiotic: protein synthesis fungicides;

glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides;

cyanoacetamideoxime fungicides; carbamate fungicides; oxidative

phosphorylation uncoupling fungicides; organo tin fungicides; carboxylic

acid fungicides; heteroaromatic fungicides; phosphonate fungicides;

phthalamic acid fungicides; benzotriazine fungicides; benzene- sulfonamide

fungicides; pyridazinone fungicides; hiophene-carboxamide fungicides;

pyrimidinamide fungicides; carboxylic acid amide (CAA) fungicides;

tetracycline antibiotic fungicides; thiocarbamate fungicides; benzamide

fungicides; host plant defense induction fungicides; and multi-site contact

activity fungicides.

9 . A method for controlling harmful pests comprising the exposure of said

harmful pests to an effective amount of the mixture according to claim 1.

10. A method according claim 9 comprising the exposure of the harmful pests,

their food supply, habitat, breeding grounds or their loci to an effective

amount of the mixture according to claim 1.

11. A method for protecting crops from attack or infestation by harmful pests

comprising the exposure of the plant, or the soil, or water in which the plant

is growing with an effective amount of the mixture according to claim 1.

12. A method according to claim 11 wherein the exposure is to the plant, plant

propagation material, part of the plant and/or plant organ that grow at a later

point in time.

13. The method according to claim 11, comprising the employment of 2 to 2000

g/ha of the mixture according to claim 1.

14. A composition comprising an effective amount of the mixture according to

claim 1 in a weight ratio of compound(I):compound(II) ranging from about

1000:1 to about 1:1000.

15. A composition according to claim 14 in a form selected among ready-to-use

solutions, emulsifiable concentrates, emulsions, suspensions, wettable

powders, soluble powders, granules, soluble granules, dispersible granules,

microemulsions, microcapsule suspensions and mixtures thereof.

16. A process for preparing a composition according to any of the claims 14 to

15, which comprise mixing compound (I) and one or more compounds (II)

with a diluent(s) and/or surfactant(s).

17. Use of the mixture according to claim 1 for controlling harmful pests.

18. Use according to claim 17 comprising the exposure of the harmful pests to

an effective amount of the mixture according to claim 1.

19. Use according claim 18 wherein the exposure is to the harmful pests, their

food supply, habitat, breeding grounds or their loci.

20. Use according to claim 18 or 19 wherein the harmful pests are exposed to a

composition according to claim 14.

21. Use of the mixture according to claim 1 for protecting crops from attack or

infestation by harmful pests comprising the exposure of the plant, plant

propagation material, part of the plant and/or plant organ that grow at a later

point in time, by applying an effective amount of the mixture on the plant,

part of the plant, plant organ, plant propagation material or a surrounding

area thereof.

22. Use according to claim 21, comprising the employment of 2 to 2000 g/ha of

the mixture according to claim 1.

International application No

PCT/DK2014/05Q243

A. CLASSIFICATION O F SUBJECT MATTERINV. AO1N53/00ADD.

According to International Patent Classification (IPC) or to both national classification and IPC

B. FIELDS SEARCHED

Minimum documentation searched (classification system followed by classification symbols

A01N

Documentation searched other than minimum documentation to the extent that such documents are included in the fields searched

Electronic data base consulted during the international search (name of data base and, where practicable, search terms used)

EPO-Internal WPI Data, BIOSIS, CHEM ABS Data

C. DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

WO 2012/040802 A2 (FMC QUIMICA DO B ASI L 1-22LTDA [BR] BORGES LUIS DONZI ETE [BR] ;FABRI CARL) 5 Apri l 2012 (2012-04-05)c l aims 1-14

/ -

X Further documents are listed in the continuation of Box C. See patent family annex.

* Special categories of cited documents :"T" later document published after the international filing date or priority

date and not in conflict with the application but cited to understand"A" document defining the general state of the art which is not considered the principle or theory underlying the invention

to be of particular relevance

"E" earlier application or patent but published on or after the international "X" document of particular relevance; the claimed invention cannot befiling date considered novel or cannot be considered to involve an inventive

"L" document which may throw doubts on priority claim(s) orwhich is step when the document is taken alonecited to establish the publication date of another citation or other " document of particular relevance; the claimed invention cannot bespecial reason (as specified) considered to involve an inventive step when the document is

"O" document referring to an oral disclosure, use, exhibition or other combined with one or more other such documents, such combinationmeans being obvious to a person skilled in the art

"P" document published prior to the international filing date but later thanthe priority date claimed "&" document member of the same patent family

Date of the actual completion of the international search Date of mailing of the international search report

6 October 2014 21/10/2014

Name and mailing address of the ISA/ Authorized officer

European Patent Office, P.B. 5818 Patentlaan 2NL - 2280 HV Rijswijk

Tel. (+31-70) 340-2040,Fax: (+31-70) 340-3016 Mari e , Geral d

International application No

PCT/DK2014/050243

C(Continuation). DOCUMENTS CONSIDERED TO BE RELEVANT

Category* Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No.

Y LIU H ET AL: "Enanti osel ecti ve 1-22cytotoxi c i t y of the i nsecti c i de b i fenthri non a human amnion epi thel i a l (FL) cel l

i ne" ,TOXICOLOGY, LIMERICK, I R,vol . 253 , no. 1-3 ,20 November 2008 (2008-11-20) , pages89-96, XP025625953,ISSN : 0300-483X, D0I :10. 1016/J .T0X.2008.08.015[retri eved on 2008-09-07]c i ted i n the appl i cati onabstracttable 1page 94, right-hand col umn, l ast paragraph

Y W0 03/053905 Al (SYNGENTA LTD [GB] ; BROWN 1-22STEPHEN MARTIN [GB] ; G0TT BRIAN DAVID[GB] ) 3 July 2003 (2003-07-03)page 1, l i nes 15-23

International application NoInformation on patent family members

PCT/DK2014/05Q243

Patent document Publication Patent family Publicationcited in search report date member(s) date

WO 2012040802 A2 05-04-2012 083215 Al 06-02-2013PI 1003434 A2 22-01-2013

33633 A 30-04-20122012040802 A2 05-04-2012

W0 03053905 Al 03-07-2003 AU 2002366752 Al 09-07-2003W0 03053905 Al 03-07-2003

WO 2015/021991 Al

Documents

Transcript of WO 2015/021991 Al